Metal-ligand complex catalyzed processes

A process for stabilizing an organophosphorus ligand against hydrolytic degradation and/or a metal-organophosphorus ligand complex catalyst against deactivation which process comprises treating a reaction product fluid containing a metal-organophosphorus ligand complex catalyst and optionally free organophosphorus ligand and which also contains one or more phosphorus acidic compounds, with an aqueous buffer solution sufficient to neutralize and remove at least some amount of said one more phosphorus acidic compounds from said reaction product fluid, wherein said reaction product fluid comprises an organic phase and said aqueous buffer solution comprises a separate aqueous phase, and wherein said organophosphorus ligand is selected from the following and said metal-organophosphorus ligand complex catalyst comprises a Group 8, 9 or 10 metal complexed with an organophosphorus ligand selected from the following:

• (i) a monoorganophosphorus ligand represented by the formula:
• ##STR14## wherein R.sup.1 represents a substituted or unsubstituted trivalent hydrocarbon radical containing from 4 to 40 carbon atoms or greater, each X' is the same or different and represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, provided at least one X' is other than a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater and at least one X' is other than an oxygen (O) atom, and each d is the same or different and is a value of 0 or 1, provided that the normal valencies of R.sup.1, X' and phosphorus (P) are satisfied;
• (ii) a diorganophosphorus ligand represented by the formula:
• ##STR15## wherein R.sup.2 represents a substituted or unsubstituted divalent hydrocarbon radical containing from 4 to 40 carbon atoms or greater, W represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 18 carbon atoms or greater, X" represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, each X' is the same or different and represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, provided at least one X' and X" is other than a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater and at least one X' and X" is other than an oxygen (O) atom, and each d is the same or different and is a value of 0 or 1, provided that the normal valencies of R.sup.2, X' and phosphorus (P) are satisfied;
• (iii) a triorganophosphorus ligand represented by the formula:
• ##STR16## wherein each R.sup.6 is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical, each X' is the same or different and represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, provided at least one X' is other than a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater and at least one X' is other than an oxygen (O) atom, and each d is the same or different and is a value of 0 or 1, provided that the normal valencies of R.sup.6, X' and phosphorus (P) are satisfied;
• and
• (iv) an organopolyphosphorus ligand containing two or more tertiary (trivalent) phosphorus atoms represented by the formula:
• ##STR17## wherein X represents a substituted or unsubstituted n-valent hydrocarbon bridging radical containing from 2 to 40 carbon atoms, each R.sup.7 is the same or different and represents a divalent hydrocarbon radical containing from 4 to 40 carbon atoms, each R.sup.8 is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, each X' is the same or different and represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, provided at least one X' is other than a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater and at least one X' is other than an oxygen (O) atom, a and b can be the same or different and each have a value of 0 to 6, with the proviso that the sum of a+b is 2 to 6 and n equals a+b, and each d is the same or different and is a value of 0 or 1, provided that the normal valencies of R.sup.7, R.sup.8, X', X and phosphorus (P) are satisfied.

A process for preventing and/or lessening hydrolytic degradation of an organophosphorus ligand and/or deactivation of a metal-organophosphorus ligand complex catalyst which process comprises treating a reaction product fluid containing a metal-organophosphorus ligand complex catalyst and optionally free organophosphorus ligand and which also contains one or more phosphorus acidic compounds, with an aqueous buffer solution sufficient to neutralize and remove at least some amount of said one or more phosphorus acidic compounds from said reaction product fluid, wherein said reaction product fluid comprises an organic phase and said aqueous buffer solution comprises a separate aqueous phase, and wherein said organophosphorus ligand is selected from the following and said metal-organophosphorus ligand complex catalyst comprises a Group 8, 9 or 10 metal complexed with an organophosphorus ligand selected from the following:

• (i) a monoorganophosphorus ligand represented by the formula:
• ##STR18## wherein R.sup.1 represents a substituted or unsubstituted trivalent hydrocarbon radical containing from 4 to 40 carbon atoms or greater, each X' is the same or different and represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, provided at least one X' is other than a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater and at least one X' is other than an oxygen (O) atom, and each d is the same or different and is a value of 0 or 1, provided that the normal valencies of R.sup.1, X' and phosphorus (P) are satisfied;
• (ii) a diorganophosphorus ligand represented by the formula:
• ##STR19## wherein R.sup.2 represents a substituted or unsubstituted divalent hydrocarbon radical containing from 4 to 40 carbon atoms or greater, W represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 18 carbon atoms or greater, X" represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, each X' is the same or different and represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, provided at least one X' and X" is other than a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater and at least one X' and X" is other than an oxygen (O) atom, and d is the same or different and is a value of 0 or 1, provided that the normal valencies of R.sup.2, X' and phosphorus (P) are satisfied;
• (iii) a triorganophosphorus ligand represented by the formula:
• ##STR20## wherein each R.sup.6 is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical, each X' is the same or different and represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, provided at least one X' is other than a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater and at least one X' is other than an oxygen (O) atom, and each d is the same or different and is a value of 0 or 1, provided that the normal valencies of R.sup.6, X' and phosphorus (P) are satisfied;
• and
• (iv) an organopolyphosphorus ligand containing two or more tertiary (trivalent) phosphorus atoms represented by the formula:
• ##STR21## wherein X represents a substituted or unsubstituted n-valent hydrocarbon bridging radical containing from 2 to 40 carbon atoms, each R.sup.7 is the same or different and represents a divalent hydrocarbon radical containing from 4 to 40 carbon atoms, each R.sup.8 is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, each X' is the same or different and represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, provided at least one X' is other than a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater and at least one X' is other than an oxygen (O) atom, a and b can be the same or different and each have a value of 0 to 6, with the proviso that the sum of a+b is 2 to 6 and n equals a+b, and each d is the same or different and is a value of 0 or 1, provided that the normal valencies of R.sup.7, R.sup.8, X', X and phosphorus (P) are satisfied.

An improved process which comprises reacting one or more reactants in the presence of a metal-organophosphorus ligand complex catalyst and optionally free organophosphorus ligand to produce a reaction product fluid comprising one or more products, the improvement comprising preventing and/or lessening hydrolytic degradation of any said organophosphorus ligand and deactivation of said metal-organophosphorus ligand complex catalyst by treating at least a portion of said reaction product fluid derived from said process and which also contains phosphorus acidic compounds formed during said process with an aqueous buffer solution sufficient to neutralize and remove at least some amount of the phosphorus acidic compounds from said reaction product fluid, wherein said reaction product fluid comprises an organic phase and said aqueous buffer solution comprises a separate aqueous phase, and wherein said organophosphorus ligand is selected from the following and said metal-organophosphorus ligand complex catalyst comprises a Group 8, 9 or 10 metal complexed with an organophosphorus ligand selected from the following:

• (i) a monoorganophosphorus ligand represented by the formula:
• ##STR22## wherein R.sup.1 represents a substituted or unsubstituted trivalent hydrocarbon radical containing from 4 to 40 carbon atoms or greater, each X' is the same or different and represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, provided at least one X' is other than a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater and at least one X' is other than an oxygen (O) atom, and each d is the same or different and is a value of 0 or 1, provided that the normal valencies of R.sup.1, X' and phosphorus (P) are satisfied;
• (ii) a diorganophosphorus ligand represented by the formula:
• ##STR23## wherein R.sup.2 represents a substituted or unsubstituted divalent hydrocarbon radical containing from 4 to 40 carbon atoms or greater, W represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 18 carbon atoms or greater, X" represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, each X' is the same or different and represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, provided at least one X' and X" is other than a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater and at least one X' and X" is other than an oxygen (O) atom, and each d is the same or different and is a value of 0 or 1, provided that the normal valencies of R.sup.2, X' and phosphorus (P) are satisfied;
• (iii) a triorganophosphorus ligand represented by the formula:
• ##STR24## wherein each R.sup.6 is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical, each X' is the same or different and represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical, a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, provided at least one X' is other than a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater and at least one X' is other than an oxygen (O) atom, and each d is the same or different and is a value of 0 or 1, provided that the normal valencies of R.sup.6, X' and phosphorus (P) are satisfied;
• and
• (iv) an organopolyphosphorus ligand containing two or more tertiary (trivalent) phosphorus atoms represented by the formula:
• ##STR25## wherein X represents a substituted or, unsubstituted n-valent hydrocarbon bridging radical containing from 2 to 40 carbon atoms, each R.sup.7 is the same or different and represents a divalent hydrocarbon radical containing from 4 to 40 carbon atoms, each R.sup.8 is the same or different and represents a substituted or unsubstituted monovalent hydrocarbon radical containing from 1 to 24 carbon atoms, each X' is the same or different and represents an oxygen (O) atom, a substituted or unsubstituted divalent nitrogen (N) atom-containing radical a substituted or unsubstituted divalent sulfur (S) atom-containing radical or a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater, provided at least one X' is other than a substituted or unsubstituted divalent hydrocarbon radical containing from 2 to 40 carbon atoms or greater and at least one X' is other than an oxygen (O) atom, a and b can be the same or different and each have a value of 0 to 6, with the proviso that the sum of a+b is 2 to 6 and n equals a+b, and each d is the same or different and is a value of 0 or 1, provided that the normal valencies of R.sup.7, R.sup.8, X', X and phosphorus (P) are satisfied.