초록 ▼

A process of hydrolyzing a monodentate, bidentate or tridentate phosphorus-based phosphite ester ligand or ligand blend for a transition metal catalyst comprising contacting the ligand or ligand blend with a hydrolysis catalyst of the formula (R11X11)nP(OH)3-n where n is 0, 1 or 2 wherein the ligand

A process of hydrolyzing a monodentate, bidentate or tridentate phosphorus-based phosphite ester ligand or ligand blend for a transition metal catalyst comprising contacting the ligand or ligand blend with a hydrolysis catalyst of the formula (R11X11)nP(OH)3-n where n is 0, 1 or 2 wherein the ligand or ligand blend comprises one or more of (i) a bidentate biphosphite ligand of formula (III), (R12—X12)(R13—X13)P—X14—Y—X24—P(X22—R22)(X23—R23), (ii) a tridentate triphosphite ligand of formula (IIIA) (R12—X12)(R13—X13)P—X14—Y—X32—P(X34—R34)—(X33—Y2—K24—P(X23—R23)—(X22—R22) or (iii) a monodentate phosphite ligand of formula (IV) P(X1—R1)(X2—R2)(X3—R3) where each X is oxygen or a bond and each Y is an optionally substituted C6-C20 arylene, followed by separation of the ligand hydrolysis products.

대표청구항 ▼

1. A process of hydrolyzing a phosphorus-based ligand for a transition metal catalyst, wherein the ligand comprises at least one phosphite ester group; the process comprising: i) contacting a hydrolysis catalyst of formula (I) (R11X11)nP(OH)3-n  (I)wherein n is 0, 1, or 2, and each X11 is independen

1. A process of hydrolyzing a phosphorus-based ligand for a transition metal catalyst, wherein the ligand comprises at least one phosphite ester group; the process comprising: i) contacting a hydrolysis catalyst of formula (I) (R11X11)nP(OH)3-n  (I)wherein n is 0, 1, or 2, and each X11 is independently oxygen or a bond, and each independently selected R11 is (C1-C10)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(C1-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(C1-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(C1-C10)alkyl of R11, each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, and (C6-C20)aryl(C1-C10)alkyl; or, when n=2, two R11 groups are optionally directly bonded to each other such that the two R11X11 groups, together with the phosphorus atom to which they are bonded, form a ring;with one or more phosphorus-based ligands selected from the group consisting of:a bidentate phosphorus-based ligand of formula (III) a tridentate phosphorus-based ligand of formula (IIIA) wherein for the ligand of formula (III), X12, X13, X14, X22, X23, and X24, each independently is oxygen or a bond, provided that at least one of X12, X13, X14, X22, X23, or X24 is oxygen, and for the ligand of formula (IIIA), X12, X13, X14, X22, X23, X24, X32, X33, and X34, each independently is oxygen or a bond, provided that at least one of X12, X13, X14, X22, X23, X24, X32, X33, or X34 is oxygen;for the ligand of formula (III), R12, R13, R22, and R23, and for the ligand of formula (IIIA), R12, R13, R22, R23, and R34, each independently is (C1-C10)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(C1-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(C1-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(C1-C10)alkyl of R12, R13, R22, R23, or R34, each ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, and (C6-C20)aryl(C1-C10)alkyl; or, optionally, one or more of pairs R12 and R13 or R22 and R23 are mutually directly bonded, such that the R12X12 and R13X13 groups, or the R22X22 and R23X23 groups, or both, together with the respective phosphorus atom to which each pair of groups is bonded, forms a respective ring;for the ligand of formula (III) the group Y, and for the ligand of formula (IIIA), the groups Y1 and Y2 independently, is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted with 1-4 (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(C1-C10)alkyl, fluorine, chlorine, bromine, or (C1-C10)haloalkyl;and a monodentate phosphorus-based ligand of formula (IV) P(X1R1)(X2R2)(X3R3)  (IV)wherein X1, X2 and X3 are each independently oxygen or a bond, provided that at least one of X1, X2, or X3 is an oxygen; and R1, R2 and R3 is each independently (C1-C10)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(C1-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(C1-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(C1-C10)alkyl of R1, R2, or R3, each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, and (C6-C20)aryl(C1-C10)alkyl; or, optionally, any two of R1, R2, or R3 are directly bonded to each other such that any pair of R1X1, R2X2, and R3X3 groups, together with the phosphorus atom to which they are bonded, forms a ring;in the presence of water and, optionally, one or more organic liquids, under conditions of time, temperature, and concentration sufficient to bring about hydrolysis of at least one phosphite ester bond to provide a hydrolysis product; andii) separating the hydrolysis catalyst and the hydrolysis product from the ligand by liquid-liquid extraction. 2. The process of claim 1, wherein R1, R2, R3, R11, R12, R13, R22, R23 or R34 is each an independently selected (C6-C20)aryl group, which is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl, or wherein one or more pair of R1 and R2, or R12 and R13, or R22 and R23, or when n=2, two R1, is directly mutually bonded such that any pair together with the respective X1, X2, X11, X12, X13, X22 or X23 groups and the phosphorus atom to which they are bonded, forms a ring. 3. The process of claim 1, wherein each independently selected R1, R2, R3, R11, R12, R13, R22, R23 or R34 is a group of formula (II) wherein a wavy line indicates a point of attachment; and wherein R45 is selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl, and each of R46, R47 and R48 is independently selected from the group consisting of H, (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl. 4. The process of claim 1 wherein Y, or independently selected Y1 or Y2, is a (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted independently with 1-4 (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(C1-C10)alkyl, fluorine, chlorine, bromine, or (C1-C10)haloalkyl. 5. The process of claim 1, wherein the hydrolysis catalyst of formula (I) is a hydrolysis product of at least one of the phosphorus-containing ligand of formula (III), (IIIA), or (IV), produced in a reaction milieu of hydrocyanation of an olefin, or is added to the reaction milieu, or both. 6. The process of claim 1, wherein the removal step ii) is through extraction between a nonpolar and a polar organic solvent. 7. The process of claim 6, wherein the nonpolar solvent comprises cyclohexane. 8. The process of claim 6, wherein the polar solvent is a raffinate from a hydrocyanation reaction of butadiene, or the polar solvent comprises adiponitrile, or both. 9. The process of claim 1, comprising the ligand of formula (III) is of formula (X): wherein each R41 and R45 is independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, and (C3-C10)cycloalkoxy(C1-C10)alkoxy, and each of R42, R43, R44, R46, R47 and R48 is independently selected from the group consisting of H, (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, and (C3-C10)cycloalkoxy(C1-C10)alkoxy. 10. The process of claim 9, wherein for the ligand of formula (X), R41 is methyl, ethyl, isopropyl, or cyclopentyl;R42 is H or methyl;R43 is H or (C1-C4)alkyl;R44 is H or methyl;R45 is methyl, ethyl, or isopropyl; andR46, R47 and R48 are independently H or (C1-C4)alkyl. 11. The process of claim 1, wherein the ligand of formula (III) is of formula (VII): wherein R17 is methyl, ethyl, or iso-propyl, and R18 and R19 are independently H or methyl. 12. The process of claim 1, wherein the ligand of formula (III) is of formula (XII) wherein R12, R13, R22 and R23 are each independently an unsubstituted or a substituted monovalent aryl, and each of RY3—RY10 is independently selected from the group consisting of hydrogen, (C1-C10) alkyl, and (C1-C10)alkoxy, or wherein two adjacent RY3—RY10 groups together form an optionally substituted fused aryl ring. 13. The process of claim 12, wherein for the ligand of formula (XII), R12, R13, R22, and R23 are each independently phenyl substituted at a respective first ortho-position with a (C1-C10)alkyl or (C1-C10)alkoxy, at a respective second ortho-position with hydrogen, and wherein respective meta- and para-positions of the R12, R13, R22, and R23 phenyls can each independently be unsubstituted or be independently substituted with 1-3 (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, or (C3-C10)cycloalkoxy(C1-C10)alkoxy. RY6 and RY10 are independently (C1-C10)alkyl or (C1-C10)alkoxy, and RY3, RY4, RY5, RY7, RY8, and RY9, are independently H, (C1-C10)alkyl, or (C1-C10)alkoxy, provided that at least one of RY3, RY4, or RY5, and at least one of RY7, RY8, or RY9, is (C1-C10)alkyl or (C1-C10)alkoxy. 14. The process of claim 1, wherein the ligand of formula (III) is of formula (V): 15. The process of claim 1 wherein the hydrolysis catalyst is of formula (IA1): or is of formula (IB1): or is a mixture thereof, wherein R45 is selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl, and each of R46, R47 and R48 is independently selected from the group consisting of H, (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl. 16. The process of claim 15, wherein in the hydrolysis catalyst of formula (IA1), (IB1), or both, R45 is methyl, ethyl or isopropyl. 17. The process of claim 15, wherein in the hydrolysis catalyst of formula (IA1), (IB1), or both, R45 is methyl, ethyl or isopropyl, R46 is hydrogen, and R47 and R48 are independently H or methyl. 18. The process of claim 1 wherein the hydrolysis catalyst has the following formula (IA2): or is of formula (IB2): or is a mixture thereof. 19. A process for modifying the relative ratio of two phosphorus-based ligands for a transition metal catalyst, wherein each ligand in the blend comprises at least one phosphite ester group, in a ligand blend comprising at least two phosphorus-based ligands, a first component of the blend being selected from the group consisting of a bidendate phosphorus-based ligand of formula (III) and a tridentate phosphorus-based ligand of formula (IIA): a bidentate phosphorus-based ligand of formula (III) a tridentate phosphorus-based ligand of formula (IIIA) wherein for the ligand of formula (III), X12, X13, X14, X22, X23, and X24, each independently is oxygen or a bond, provided that at least one of X12, X13, X14, X22, X23, or X24 is oxygen, and for the ligand of formula (IIIA), X12, X13, X14, X22, X23, X24, X32, X33, and X34, each independently is oxygen or a bond, provided that at least one of X12, X13, X14, X22, X23, X24, X32, X33, or X34 is oxygen;for the ligand of formula (III), R12, R13, R22, and R23, and for the ligand of formula (IIIA), R12, R13, R22, R23, and R34, each independently is (C1-C10)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(C1-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(C1-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(C1-C10)alkyl of R12, R13, R22, R23, or R34, each ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, and (C6-C20)aryl(C1-C10)alkyl; or, optionally, one or more of pairs R12 and R13 or R22 and R23 are mutually directly bonded, such that the R12X12 and R13X13 groups, or the R22X22 and R23X23 groups, or both, together with the respective phosphorus atom to which each pair of groups is bonded, forms a respective ring;for the ligand of formula (III) the group Y, and for the ligand of formula (IIIA), the groups Y1 and Y2 independently, is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted with 1-4 (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(C1-C10)alkyl, fluorine, chlorine, bromine, or (C1-C10)haloalkyl; a second component of the blend being a monodentate phosphorus-based ligand of formula (IV) P(X1R1)(X2R2)(X3R3)  (IV)wherein X1, X2 and X3 are each independently oxygen or a bond, provided that at least one of X1, X2, or X3 is an oxygen; and R1, R2 and R3 is each independently (C1-C10)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(C1-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(C1-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(C1-C10)alkyl of R1, R2, or R3, each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, and (C6-C20)aryl(C1-C10)alkyl; or, optionally, any two of R1, R2, or R3 are directly bonded to each other such that any pair of R1X1, R2X2, and R3X3 groups, together with the phosphorus atom to which they are bonded, forms a ring; and, the process comprising: i) selectively hydrolyzing a phosphite ester group of the second component of the ligand blend with respect to a phosphite ester group of the first component of the ligand blend, by contacting the blend with a hydrolysis catalyst of formula (I) (R11X11)nP(OH)3-n  (I)wherein n is 0, 1, or 2, and each X11 is independently oxygen or a bond, and each independently selected R11 is (C1-C10)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(C1-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(C1-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(C1-C10)alkyl of R11, each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, and (C6-C20)aryl(C1-C10)alkyl; or, when n=2, two R11 groups are optionally directly bonded to each other such that the two R11X11 groups, together with the phosphorus atom to which they are bonded, form a ring; in the presence of water and, optionally, one or more organic liquids, under conditions of time, temperature, and concentration sufficient to bring about hydrolysis of the at least one phosphite ester bond of the second component to provide a hydrolysis product, and ii) separating the hydrolysis catalyst and the hydrolysis product from the ligand blend by liquid-liquid extraction. 20. The process of claim 19, wherein R1, R2, R3, R11, R12, R13, R22, R23 or R34 is each an independently selected (C6-C20)aryl group, which is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl, or wherein one or more pair of R1 and R2, or R12 and R13, or R22 and R23, or when n=2, two R11, is directly mutually bonded such that any pair together with the respective X1, X2, X11, X12, X13, X22 or X23 groups and the phosphorus atom to which they are bonded, forms a ring. 21. The process of claim 19, wherein each independently selected R1, R2, R3, R11, R12, R13, R22, R23 or R34 is a group of formula (II) wherein a wavy line indicates a point of attachment; and wherein R45 is selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl, and each of R46, R47 and R48 is independently selected from the group consisting of H, (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl. 22. The process of claim 19 wherein Y, or independently selected Y1 or Y2, is a (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted independently with 1-4 (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(C1-C10)alkyl, fluorine, chlorine, bromine, or (C1-C10)haloalkyl. 23. The process of claim 19, wherein the hydrolysis catalyst of formula (I) is a hydrolysis product of at least one of the phosphorus-containing ligand of formula (III), (IIIA), or (IV), produced in a reaction milieu of hydrocyanation of an olefin, or is added to the reaction milieu, or both. 24. The process of claim 19, wherein the removal step ii) is through extraction between a nonpolar and a polar organic solvent. 25. The process of claim 24, wherein the nonpolar solvent comprises cyclohexane. 26. The process of claim 24, wherein the polar solvent is a raffinate from the hydrocyanation reaction of butadiene, comprises adiponitrile, or both. 27. The process of claim 19, comprising the ligand of formula (III) is of formula (X): wherein each R41 and R45 is independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, and (C3-C10)cycloalkoxy(C1-C10)alkoxy, and each of R42, R43, R44, R46, R47 and R48 is independently selected from the group consisting of H, (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, and (C3-C10)cycloalkoxy(C1-C10)alkoxy. 28. The process of claim 27, wherein for the ligand of formula (X), R41 is methyl, ethyl, isopropyl, or cyclopentyl;R42 is H or methyl;R43 is H or (C1-C4)alkyl;R44 is H or methyl;R45 is methyl, ethyl, or isopropyl; andR46, R47 and R48 are independently H or (C1-C4)alkyl. 29. The process of claim 19, wherein the ligand of formula (III) is of formula (VII): wherein R17 is methyl, ethyl or iso-propyl, and R18 and R19 are independently H or methyl. 30. The process of claim 19, wherein the ligand of formula (III) is of formula (XII) wherein R12, R13, R22 and R23 are each independently an unsubstituted or a substituted monovalent aryl, and each of RY3—RY10 is independently selected from the group consisting of hydrogen, (C1-C10) alkyl, and (C1-C10)alkoxy, or wherein two adjacent RY3—R10 groups together form an optionally substituted fused aryl ring. 31. The process of claim 30, wherein R12, R13, R22, and R23 are each independently phenyl substituted at a respective first ortho-position with a (C1-C10)alkyl or (C1-C10)alkoxy, at a respective second ortho-position with hydrogen, and wherein respective meta- and para-positions of the R12, R13, R22, and R23 phenyls can each independently be unsubstituted or be independently substituted with 1-3 (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, or (C3-C10)cycloalkoxy(C1-C10)alkoxy; RY6 and RY10 are independently (C1-C10)alkyl or (C1-C10)alkoxy, and RY3, RY4, RY5, RY7, RY8, and RY9, are independently H, (C1-C10)alkyl, or (C1-C10)alkoxy, provided that at least one of RY3, RY4, or RY5, and at least one of RY7, RY8, or RY9, is (C1-C10)alkyl or (C1-C10)alkoxy. 32. The process of claim 19, wherein the ligand of formula (III) is of formula (V): 33. The process of claim 19 wherein the hydrolysis catalyst is of formula (IA1): or is of formula (IB1): or is a mixture thereof, wherein R45 is selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl, and each of R46, R47 and R48 is independently selected from the group consisting of H, (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl. 34. The process of claim 33, wherein in the hydrolysis catalyst of formula (IA1), (IB1), or both, R45 is methyl, ethyl, or isopropyl. 35. The process of claim 33, wherein in the hydrolysis catalyst of formula (IA1), (IB1), or both, R45 is methyl, ethyl or isopropyl, R46 is hydrogen, and R47 and R48 are independently H or methyl. 36. The process of claim 19 wherein the hydrolysis catalyst has the following formula formula (IA2): or is of formula (IB2): or is a mixture thereof. 37. The method of claim 19, wherein the bidentate ligand of formula (III) is formula (V), and the monodentate ligand is of formula (XIII) or is of formula (XIV): or is a mixture thereof;and the hydrolysis catalyst is of the formula (IA2): or is of formula (IB2): or is a mixture thereof. 38. The process of claim 23, wherein the reaction milieu further comprises cyclohexane and/or toluene. 39. The process of claim 23, wherein the reaction milieu further comprises one or more nitriles. 40. The process of claim 39, wherein the nitriles comprise 3-pentenenitrile. 41. The process of claim 39, wherein the nitriles comprise adiponitrile. 42. A process for maintaining a concentration of a phosphorus-based bidentate ligand or of a phosphorus-based tridentate ligand, or both, within a concentration range, in a phosphorus-based ligand blend further comprising a monodentate phosphorus-based ligand, for a transition metal catalytic complex in a hydrocyanation reaction milieu comprising water and at least one organic liquid, wherein each phosphorus-based ligand in the blend comprises at least one phosphite ester group, the ligand blend comprising at least two phosphorus-based ligands, a first component of the ligand blend being a bidendate phosphorus-based ligand of formula (III) or a tridentate phosphorus-based ligand of formula (IIIA): a bidentate phosphorus-based ligand of formula (III) a tridentate phosphorus-based ligand of formula (IIIA) wherein for the ligand of formula (III), X12, X13, X14, X22, X23, and X24, each independently is oxygen or a bond, provided that at least one of X12, X13, X14, X22, X23, or X24 is oxygen, and for the ligand of formula (IIIA), X12, X13, X14, X22, X23, X24, X32, X33, and X34, each independently is oxygen or a bond, provided that at least one of X12, X13, X14, X22, X23, X24, X32, X33, or X34 is oxygen;for the ligand of formula (III), R12, R13, R22, and R23, and for the ligand of formula (IIIA), R12, R13, R22, R23, and R34, each independently is (C1-C10)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(C1-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(C1-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(C1-C10)alkyl of R12, R13, R22, R23, or R34, each ring thereof is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, and (C6-C20)aryl(C1-C10)alkyl; or, optionally, one or more of pairs R12 and R13 or R22 and R23 are mutually directly bonded, such that the R12X12 and R13X13 groups, or the R22X22 and R23X23 groups, or both, together with the respective phosphorus atom to which each pair of groups is bonded, forms a respective ring;for the ligand of formula (III) the group Y, and for the ligand of formula (IIIA), the groups Y1 and Y2 independently, is an (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted with 1-4 (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(C1-C10)alkyl, fluorine, chlorine, bromine, or (C1-C10)haloalkyl; and,a second component of the blend being a monodentate phosphorus-based ligand of formula (IV) P(X1R1)(X2R2)(X3R3)  (IV)wherein X1, X2 and X3 are each independently oxygen or a bond, provided that at least one of X1, X2, or X3 is an oxygen; and R1, R2 and R3 is each independently (C1-C10)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(C1-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(C1-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(C1-C10)alkyl of R1, R2, or R3, each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, and (C6-C20)aryl(C1-C10)alkyl; or, optionally, any two of R1, R2, or R3 are directly bonded to each other such that any pair of R1X1, R2X2, and R3X3 groups, together with the phosphorus atom to which they are bonded, forms a ring;the process comprising:i) contacting the ligand blend in the hydrocyanation reaction milieu with a hydrolysis catalyst of formula (I) (R1X11)nP(OH)3-n  (I)wherein n is 0, 1, or 2, and each X11 is independently oxygen or a bond, and each independently selected R11 is (C1-C10)alkyl, (C3-C10)cycloalkyl, (C3-C10)cycloalkyl(C1-C10)alkyl, (C6-C20)aryl, or (C6-C20)aryl(C1-C10)alkyl, wherein for any (C6-C20)aryl or (C6-C20)aryl(C1-C10)alkyl of R11, each ring thereof is independently unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, and (C6-C20)aryl(C1-C10)alkyl; or, when n=2, two R11 groups are optionally directly bonded to each other such that the two R11X11 groups, together with the phosphorus atom to which they are bonded, form a ring;such that selective hydrolysis of a phosphite ester group of the monodentate ligand of formula (IV) in the ligand blend with respect to hydrolysis of a phosphite ester group of the bidentate ligand of formula (III) or the tridentate ligand of formula (IIIA) in the ligand blend occurs, to provide a hydrolysis product; and,ii) separating the hydrolysis catalyst and the hydrolysis product from the ligand blend by liquid-liquid extraction, such that a concentration of the bidentate ligand is maintained within the concentration range. 43. The process of claim 42, wherein R1, R2, R3, R11, R12, R13, R22, R23 or R34 is each an independently selected (C6-C20)aryl group, which is unsubstituted or is substituted with 1-4 substituents independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl, or wherein one or more pair of R1 and R2, or R12 and R13, or R22 and R23, or when n=2, two R11, is directly mutually bonded such that any pair together with the respective X1, X2, X11, X12, X13, X22 or X23 groups and the phosphorus atom to which they are bonded, forms a ring. 44. The process of claim 42, wherein each independently selected R1, R2, R3, R11, R12, R13, R22, R23 or R34 is a group of formula (II) wherein a wavy line indicates a point of attachment; and wherein R45 is selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl, and each of R46, R47 and R48 is independently selected from the group consisting of H, (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl. 45. The process of claim 42 wherein Y, or independently selected Y1 or Y2, is a (C6-C20)arylene group, wherein each ring thereof is independently unsubstituted or is substituted independently with 1-4 (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryl(C1-C10)alkyl, fluorine, chlorine, bromine, or (C1-C10)haloalkyl. 46. The process of claim 42, wherein the hydrolysis catalyst of formula (I) is a hydrolysis product of at least one of the phosphorus-containing ligand of formula (III), (IIIA), or (IV), produced in a reaction milieu of hydrocyanation of an olefin, or is added to the reaction milieu, or both. 47. The process of claim 42, wherein the removal step ii) is through extraction between a nonpolar and a polar organic solvent. 48. The process of claim 47, wherein the nonpolar solvent comprises cyclohexane. 49. The process of claim 47, wherein the polar solvent is a raffinate from the hydrocyanation reaction of butadiene, comprises adiponitrile, or both. 50. The process of claim 42, comprising the ligand of formula (III) is of formula (X): wherein each R41 and R45 is independently selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, and (C3-C10)cycloalkoxy(C1-C10)alkoxy, and each of R42, R43, R44, R46, R47 and R48 is independently selected from the group consisting of H, (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, and (C3-C10)cycloalkoxy(C1-C10)alkoxy. 51. The process of claim 50, wherein for the ligand of formula (X), R41 is methyl, ethyl, isopropyl, or cyclopentyl;R42 is H or methyl;R43 is H or (C1-C4)alkyl;R44 is H or methyl;R45 is methyl, ethyl, or isopropyl; andR46, R47 and R48 are independently H or (C1-C4)alkyl. 52. The process of claim 42, wherein the ligand of formula (III) is of formula (VII): wherein R17 is methyl, ethyl or iso-propyl, and R18 and R19 are independently H or methyl. 53. The process of claim 42, wherein the ligand of formula (III) is of formula (XII) wherein R12, R13, R22 and R23 are each independently an unsubstituted or a substituted monovalent aryl, and each of RY3—RY10 is independently selected from the group consisting of hydrogen, (C1-C10) alkyl, and (C1-C10)alkoxy, or wherein two adjacent RY3—RY10 groups together form an optionally substituted fused aryl ring. 54. The process of claim 53, wherein R12, R13, R22, and R23 are each independently phenyl substituted at a respective first ortho-position with a (C1-C10)alkyl or (C1-C10)alkoxy, at a respective second ortho-position with hydrogen, and wherein respective meta- and para-positions of the R12, R13, R22, and R23 phenyls can each independently be unsubstituted or be independently substituted with 1-3 (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, or (C3-C10)cycloalkoxy(C1-C10)alkoxy; RY6 and RY10 are independently (C1-C10)alkyl or (C1-C10)alkoxy, and RY3, RY4, RY5, RY7, RY8, and RY9, are independently H, (C1-C10)alkyl, or (C1-C10)alkoxy, provided that at least one of RY3, RY4, or RY5, and at least one of RY7, RY8, or RY9, is (C1-C10)alkyl or (C1-C10)alkoxy. 55. The process of claim 42, wherein the ligand of formula (III) is of formula (V): 56. The process of claim 42 wherein the hydrolysis catalyst is of formula (IA1): or is of formula (IB1): or is a mixture thereof; wherein R45 is selected from the group consisting of (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl, and each of R46, R47 and R48 is independently selected from the group consisting of H, (C1-C10)alkyl, (C3-C10)cycloalkyl, (C1-C10)alkoxy, (C3-C10)cycloalkoxy, (C3-C10)cycloalkyl(C1-C10)alkyl, (C3-C10)cycloalkoxy(C1-C10)alkyl, (C3-C10)cycloalkyl(C1-C10)alkoxy, (C3-C10)cycloalkoxy(C1-C10)alkoxy, and (C6-C20)aryl. 57. The process of claim 56, wherein in the hydrolysis catalyst of formula (IA1), (IB1), or both, R45 is methyl, ethyl, or isopropyl. 58. The process of claim 56, wherein in the hydrolysis catalyst of formula (IA1), (IB1), or both, R45 is methyl, ethyl, or isopropyl, R46 is hydrogen, and R47 and R48 are independently hydrogen or methyl. 59. The process of claim 42 wherein the hydrolysis catalyst has the following formula formula (IA2): or is of formula (IB2): or is a mixture thereof. 60. The method of claim 42, wherein the bidentate ligand of formula (III) is formula (V), and the monodentate ligand is of formula (XIII) or is of formula (XIV): or is a mixture thereof;and the hydrolysis catalyst is of the formula (IA2): or is of formula (IB2): or is a mixture thereof. 61. The process of claim 42, wherein the reaction milieu further comprises cyclohexane and/or toluene. 62. The process of claim 42, wherein the reaction milieu further comprises one or more nitriles. 63. The process of claim 62, wherein the nitriles comprise 3-pentenenitrile. 64. The process of claim 62, wherein the nitriles comprise adiponitrile.