M. Bennett, Christopher J. Cobley, A. Rae
Mar 21, 2000
Citations
0
Influential Citations
27
Citations
Journal
Organometallics
Abstract
(Alkynyl)diphenylphosphines Ph2PC⋮CR (R = H, Me, Ph, PPh2) undergo double insertion into the nickel(0)−benzyne bond of the complexes [Ni{(1,2-η)-4,5-X2C6H2}(PEt3)2] (X = H (1a), F (1b)) to give mixtures of nickel(0) complexes containing (diphenylphosphino)naphthalenes, which in some cases are formed with high regioselectivity. Bromination of the mixtures of nickel(0) complexes obtained from Ph2PC⋮CR (R = Me, Ph) and 1a or 1b gives in high yield the chelate NiBr2 complexes [NiBr2{6,7-X2C10H2-1,4-Y2-2,3-(PPh2)2}] (X = H, Y = Me (6a), Ph (11a); X = F, Y = Me (6b), Ph (11b)), from which the corresponding 1,4-disubstituted 2,3-naphthylenebis(diphenylphosphines) 12a, 13a, 12b, and 13b can be liberated by treatment with NaCN in DMSO at 60 °C or dimethylglyoxime/ammonia at room temperature. Derivatives in which only one of the phosphorus atoms is oxidized, 6,7-X2C10H2-1,4-Me2-2-PPh2-3-P(O)PPh2 (X = H (15a), F (15b)), have also been prepared. The regioselectivity of the reactions of Ph2PC⋮CH with 1b is poorer than...