Molybdenum carbonyl complexes of diphenylphosphinous acid and diphenylphosphinous acid derivatives. Crystal and molecular structures of [Et4N][Mo(CO)4(PPh2O)2H]·0.37 CH2Cl2, Mo(CO)4(PPh2OH)(PPh2OCH2CH2NMe2)·H2O and Mo(CO)4(PPh2SPPh2)

Abstract Crystal and molecular structures for the three complexes [Et 4 N][Mo(CO) 4 (PPh 2 O) 2 H]·0.37CH 2 Cl 2 ( 1 ), [Mo(CO) 4 (PPh 2 OH)(PPh 2 OCH 2 CH 2 NMe 2 ]·H 2 O ( 2 ) and [Mo(CO) 4 (PPh 2 SPPh 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 2 PO − ligands as evidence by a short OO distance of 2.415(4) A. In complex 2 , the acidic proton of the PPh 2 OH ligand forms a strong hydrogen bond to the tertiary amine with a NO distance of 2.77 A. 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) A; the MP distances range from 2.487(2) to 2.563(2) A and average to 2.51(1) A. Compound 1 crystallizes in space group P 1 with a = 12.456(2) A, b = 13.757(3) A, c = 11.892(3) A, α = 95.51(2)° β = 108.30(2)°, γ = 91.91(1)°, V = 1922(2) A 3 , Z = 2. Compound 2 crystallizes in space group Pbca with a = 20.901(3) A, b = 16.032(3) A, c = 19.686(5) A, V = 6597(2) A 3 , Z = 8. Compound 3 crytallizes in space group P2 1 2 1 2 1 with a = 11.014(1) A, b = 14.244(2) A, c = 17.233(1) A, V = 27041(1) A 3 , Z = 4.