Synthesis of some phosphino- and arsinobenzenechromium tricarbonyl derivatives and metal carbonyl clusters

Abstract

The synthesis of a number of new phosphino- and arsinobenzenechromium tricarbonyl ligands ER2C6H5Cr(CO)3 (ER2 = PEt2, PPri2, PBut2, PPh2, AsPh2 AsMe2), ER[C6H5Cr(CO)3]2 (ER = PEt, PBut, PPh, AsPh) has been achieved by reacting lithium derivatives of benzenechromium tricarbonyl with appropriate chlorphosphines or iodoarsines. The spectroscopic properties of these ligands are described. The structure of Pri2PC6H5Cr(CO)3 was determined by an X-ray crystallographic study. This is the first solid state structure to be reported for a phosphinobenzenechromium tricarbonyl derivative. The structures of four metal carbonyl cluster complexes were also determined. Crystals of Pri2PC6H5Cr(CO)3 (3, C15H19CrO3P) are monoclinic, space group P21/c, a = 8.150(2) Å, b = 13.490(2) Å, c = 15.125(1) Å, β = 100.19(1)°, Z = 4; those of Ru3(CO)11[PPri2C6H5Cr(CO)3] (15, C26H19CrO14PRu3) are monoclinic, space group P21/n, a = 8.565(2) Å, b = 21.808(3) Å, c = 17.167(3) Å, β = 97.41(2)°, Z = 4; those of Ru3(CO)10[PPh2C6H5Cr(CO)3]2 (19, C32H15CrO14PRu3) are orthorhombic, space group Pbca, a = 17.367(4) Å, b = 24.471(5) Å, c = 16.096(3) Å, Z = 8; those of Ru3(CO)10[PPri2C6H5Cr(CO)3]2•CH2Cl2 (16, C40H38Cr2O16P2Ru3•CH2Cl2) are orthorhombic, space group P21212, a = 13.832(3) Å, b = 17.558(2) Å, c = 10.144(1) Å, Z = 2; and those of Os3(CO)9[PEt2C6H5Cr(CO)3]3 (26, C48H45Cr3O18Os3P3) are trigonal, space group [Formula: see text], a = 15.7558(4) Å, c = 12.662(1) Å, Z = 2. The structures were solved by the Patterson method and were refined by full-matrix least-squares procedures to R = 0.031,0.027, 0.029, 0.025, and 0.029 (Rw = 0.027, 0.024, 0.024, 0.023, and 0.025) for 2326, 4110, 3878, 3046, and 4093 reflections with I ≥ 3σ(I), respectively. Key words: metal carbonyl clusters, phosphinobenzenechromium tricarbonyl derivatives, arsinobenzenechromium tricarbonyl derivatives, crystal structures.