Phosphine, arsine and stibine complexes of manganese(I) carbonyl halides: synthesis, multinuclear NMR spectroscopic studies, redox properties and crystal structures

A crystallographic and spectroscopic investigation of the stereochemistry of [MBr(CO)3L2] (M=Mn, Re) complexes: crystal and molecular structures of [MBr(CO)3L2] {M=Mn, L=P(C6H4Cl-4)3, 1/2dppe, 1/2dppf; M=Re, L=P(C6H4OMe-4)3, 1/2dppf}

“…The structures of all the compounds can be seen as octahedral or distorted octahedral with fac ,cis geometries for 4, 6, 8, and 12, and a mer ,trans geometry for 1. The molecular structure reported here for 4, as its solvate 4 ×/CHCl 3 , is very similar to that previously reported [9] for 4×/1/2CHCl 3 but unit cell parameters and Z values are very different. Bond lengths and bond angles may be appropriately compared to previously structurally characterised bromotricarbonyl Mn(I) and Re(I) P-donor ligand derivatives: 4 ×/1/2CHCl 3 [9], fac ,cis -[MBr(CO) 3 L 2 ] {M0/Mn, L 0/PPhH 2 , PPh(OMe) 2 [9,12] M 0/Re, L 0/PPh 2 (OEt), 1/2h 2 -CH 3 C(CH 2 PPh 2 ) 3 , 1/2C 6 H 4 P(CH 2 OH) 2 [19 Á/21]} and mer ,trans -[MnBr(CO) 3 {PPh(OMe) 2 } 2 ] [12].…”

“…The molecular structure reported here for 4, as its solvate 4 ×/CHCl 3 , is very similar to that previously reported [9] for 4×/1/2CHCl 3 but unit cell parameters and Z values are very different. Bond lengths and bond angles may be appropriately compared to previously structurally characterised bromotricarbonyl Mn(I) and Re(I) P-donor ligand derivatives: 4 ×/1/2CHCl 3 [9], fac ,cis -[MBr(CO) 3 L 2 ] {M0/Mn, L 0/PPhH 2 , PPh(OMe) 2 [9,12] M 0/Re, L 0/PPh 2 (OEt), 1/2h 2 -CH 3 C(CH 2 PPh 2 ) 3 , 1/2C 6 H 4 P(CH 2 OH) 2 [19 Á/21]} and mer ,trans -[MnBr(CO) 3 {PPh(OMe) 2 } 2 ] [12]. The chloro compounds [MnCl(CO) 3 (dppf)] and [ReCl(CO) 3 (dppf)], which are closely related to 6 and 12 have also been characterized crystallographically [22,23].…”

“…The Mn Ã/Br distances in compounds 4 and 6 ranged from 2.5068(8) Á/2.5198(10) Å , and were significantly larger than those found for the mer ,trans derivative 1 (2.5458(7) Å ). These distances for 4×/ CHCl 3 and 6 were within error of those observed for these distances in 4×/1/2CHCl 3 [9] and fac ,cis -[MnBr(CO) 3 (PPhH 2 ) 2 ] [9]. The Re Ã/Br distances in compounds 8 and 12, were as expected longer, and ranged from 2.586 (3) (6), av.…”

“…The fac ,cis-configuration is also likely to be obtained for Mn(I) derivatives with bidentate organophosphine ligands and complexes 4 Á/6 are assigned this configuration, with the structures of 4 ×/ CHCl 3 and 6 confirmed by crystallographic studies. A recent publication by Pope and Reid [9] has reported the synthesis of 4 and also describes an X-ray structure of 4×/ 1/2CHCl 3 . The structures of the [MnBr(CO) 3 L 2 ] complexes with two monodentate organophosphine ligands usually have either fac ,cis -or mer ,trans-stereochemistry, and their relative stabilities must be very similar since Kruger et al [12] have isolated and crystallographically characterised both isomers for [MnBr(CO) 3 {P-Ph(OMe) 2 } 2 ].…”

Crystal structure of tricarbonylbis[1,2-(diphenylphosphino)benzene]-manganese(I) bromide, Mn(CO)3(C30H24P2)Br

“…The title complex belongs to the group of manganese and rhenium carbonyl halide complexes which have attracted interest due to their unusual electrochemical properties and spectroscopic characterisations [1,4,5]. fac-[Mn(CO) 3(dppbz)Br] (dppbz = C 30 H 24 P 2 )isofinterest for us due to the bio-activity shown by transition metal carbonyl halide complexes containing arsenic, phosphorus or sulfur ligands [6,7].…”