Reactions of the nickel-tungsten unsaturated species (.eta.-C5Me5)Ni-W(CO)3(.eta.-C5H5) and of its methylene derivative (.eta.-C5Me5)Ni(.mu.-CO)(.mu.-CH2)W(CO)2(.eta.-C5H5) with two-electron donors

Reactions of Unsaturated Nickel–Molybdenum and –Tungsten Complexes with Primary Amines: Chemoselective N‐Coordination to Nickel To Give the First Structurally Characterised Primary Amine–Organonickel Complexes

“…The complex [(η-C 5 Me 5 )Ni-ត Mo(CO) 3 (η-C 5 H 5 )] (1a) is both heterodimetallic and unsaturated. It can also be formulated as [(η-C 5 Me 5 )Ni(µ-CO)Mo(CO) 2 (η-C 5 H 5 )]-(Ni=Mo) (1a) and can be considered to contain a formal Ni=Mo double bond.…”

“…It can also be formulated as [(η-C 5 Me 5 )Ni(µ-CO)Mo(CO) 2 (η-C 5 H 5 )]-(Ni=Mo) (1a) and can be considered to contain a formal Ni=Mo double bond. [1] Despite the rich chemistry exhibited by 1a, [2,3] some of its simple coordination chemistry has still not yet been fully investigated.…”

“…Complex 2a (C 21 to this complex and to its Ni-W analogue 1b. [5] Structural data have so far been restricted to the allyldiphenylphosphane adduct of 1a [6] and show that the group 15 donor ligand is indeed bonded to the molybdenum atom. Spectroscopic data on Ni-W analogues of 1a with other phosphane ligands, notably the magnitude of the 183 W-31 P coupling, indicate that two-electron donor phosphorus ligands such as PMe 3 and PMe 2 Ph, coordinate to the group 6 metal atom (Scheme 1).…”

“…Spectroscopic data on Ni-W analogues of 1a with other phosphane ligands, notably the magnitude of the 183 W-31 P coupling, indicate that two-electron donor phosphorus ligands such as PMe 3 and PMe 2 Ph, coordinate to the group 6 metal atom (Scheme 1). [5] Reactions of 1a and related Ni-W analogues with potentially bridging ligands (CO, tBuNC, CH 2 , SO 2 ) afford complexes in which the ligand is either bridging (CH 2 , SO 2 ) [5,7,8] or else undergoes rapid bridge/terminal exchange (CO, tBuNC, Scheme 1). [5,7] For the tBuNC adduct NiW(CO) 3 (tBuNC)(η-C 5 H 5 )(η-C 5 Me 5 ) resonances for isomers with bridging or with terminal tBuNC groups were observed in the IR spectrum.…”

“…[5] Reactions of 1a and related Ni-W analogues with potentially bridging ligands (CO, tBuNC, CH 2 , SO 2 ) afford complexes in which the ligand is either bridging (CH 2 , SO 2 ) [5,7,8] or else undergoes rapid bridge/terminal exchange (CO, tBuNC, Scheme 1). [5,7] For the tBuNC adduct NiW(CO) 3 (tBuNC)(η-C 5 H 5 )(η-C 5 Me 5 ) resonances for isomers with bridging or with terminal tBuNC groups were observed in the IR spectrum. [5] Never having previously observed terminal ligand coordination to the nickel atom, we believed that amine adducts of 1a would also contain Mo-N bonds.…”