Molybdenum carbonyl complexes of diphenylphosphinous acid and diphenylphosphinous acid derivatives. Crystal and molecular structures of [Et 4N][Mo(CO) 4(PPh 2O) 2H]·0.37 CH 2Cl 2, Mo(CO) 4(PPh 2OH)(PPh 2OCH 2CH 2NMe 2)·H 2O and Mo(CO) 4(PPh 2SPPh 2)

Abstract

Crystal and molecular structures for the three complexes [Et 4N][Mo(CO) 4(PPh 2O) 2H]·0.37CH 2Cl 2 ( 1), [Mo(CO) 4(PPh 2OH)(PPh 2OCH 2CH 2NMe 2]·H 2O ( 2) and [Mo(CO) 4(PPh 2SPPh 2] ( 3) are reported. The octahedral coordination sphere at molybdenum consists of four carbonyl groups and two cis oriented phosphorus donor ligands. The unlocated hydrogen atom in 1 forms a strong hydrogen bridge between the two Ph 2PO − ligands as evidence by a short OO distance of 2.415(4) Å. In complex 2, the acidic proton of the PPh 2OH ligand forms a strong hydrogen bond to the tertiary amine with a NO distance of 2.77 Å. Complex 3 has essentially C 2v symmetry; the PSP bond angle is 86.9°. The PMP angles are 88.06(4)°, 86.36(7)° and 72.02(7)° for 1, 2 and 3, respectively. The average MC distance over all these compounds is 2.010(6) Å; the MP distances range from 2.487(2) to 2.563(2) Å and average to 2.51(1) Å. Compound 1 crystallizes in space group P 1 with a = 12.456(2) Å, b = 13.757(3) Å, c = 11.892(3) Å, α = 95.51(2)° β = 108.30(2)°, γ = 91.91(1)°, V = 1922(2) Å 3, Z = 2. Compound 2 crystallizes in space group Pbca with a = 20.901(3) Å, b = 16.032(3) Å, c = 19.686(5) Å, V = 6597(2) Å 3, Z = 8. Compound 3 crytallizes in space group P2 12 12 1 with a = 11.014(1) Å, b = 14.244(2) Å, c = 17.233(1) Å, V = 27041(1) Å 3, Z = 4.