Oxygen atom transfer from nitrogenous ReVO reagents to diphosphines and subsequent transformations.: Rhenium(III) products and reaction models

The concerned diphosphines are Ph2P(CH2)(n)PPh2 (1), abbreviated PnP, and the (ReO)-O-V reagents are RcOCl(3)L (2) and ReOCl3L' (3), where L and L' are the azopyridine and pyridine-imine ligands p-ClC6H4N=NC5H4N and p-MeC6H4N=CHC5H4N, respectively. One atom transfer from 2 to 1 has afforded Re(OPnP)Cl3L (4a, n = 1; 4b, n = 2:, 4c, n = 3). Of these 4b and 4c are stable, but 4a undergoes spontaneous isomerization to Re(PlPO)Cl3L (5) in solution. Two-atom transfer studied with both 2 and 3 has afforded binuclear LCl3Re(OPnPO)ReCl3L (8a, n = 2; 8b, n = 3) and L'Cl3Re(OPnPO)ReCl3L' (9a, n = 2; 9b, n = 3) for n = 2, 3 and mononuclear Re(OP1PO)Cl3L (11) and Re(OP1PO)Cl3L' (12) for n = 1. The mixed system L'Cl3Re(OP2PO)RcCl(3)L (10) has been prepared from 3 and 4b. The complex Re(PPh3)Cl3L (7a) is furnished by the reaction of Re(OPPh3)Cl3L (6a) or 4b or 11 with PPh3. The species have been characterized with the help of spectral, electrochemical, and X-ray structural data. All the complexes have mer geometry except 5 and 7a, which have fac geometry. The latter is best suited for concurrent Re-N and Re-P back-bonding. Variable-temperature rate data of the reaction 4a --> 5 are consistent with an intramolecular strongly associative transition state (DeltaS(double dagger), -22.6 eu) in which the dangling phosphine function lies close to the metal. Two-atom transfer to PIP is believed to proceed via a transient binuclear intermediate which undergoes cleavage at one end due to steric crowding, affording 11 and 12. Crystal data for the complexes are as follows: 5(.)1.5 C6H6. empirical formula C45H39Cl4N3OP2Re, crystal system triclinic, are as follows: 5(.)1.5 C6H(6), empirical formula C45H39Cl4N3OP2Re, crystal system triclinic space group P (1) over bar, a = 10.034(2) Angstrom, b = 10.737(2) Angstrom, c = 20.357(4) Angstrom, alpha = 89.38(3)degrees, beta = 87.79(3)degrees, gamma = 80.22(3)degrees, V= 2159.7(7) Angstrom (3), Z = 2; 7a(.)CH(2)Cl(2), empirical formula C30H325Cl6N3PRe, crystal system monoclinic, space group P2(1)/n, n = 11.695(6) Angstrom, b = 17.745(7) Angstrom, c = 15.359(9) Angstrom, beta = 100.93(5)degrees, V = 3150(3) Angstrom (3), Z = 4; 9a, empirical formula C52H48Cl6N4O2P2Re2, crystal system monoclinic, space group C2/c, n = 19.764(12) A, b = 12.863(6) Angstrom, c = 22,20(2) Angstrom, beta = 101.76(6)degrees, V = 5530(6) Angstrom (3), Z = 3; 11, empirical formula C36H30Cl4N3O2P2Re, crystal system monoclinic, space group I2/n, a = 16.866(6) Angstrom, b = 12.583(6) Angstrom, c = 34.38(2) Angstrom, beta = 99.22(4)degrees, V= 7285(7) Angstrom (3), Z = 8.