452956-52-4Relevant academic research and scientific papers
Ligand-induced and reductively induced alkyne-isocyanide coupling reactions of Mo(CnBut)3(PhC≡CPh)(η5-C5M e55)][BF4]
Adams, Christopher J.,Anderson, Kirsty M.,Bartlett, Ian M.,Connelly, Neil G.,Orpen, A. Guy,Paget, Timothy J.
, p. 3454 - 3463 (2002)
The complex [Mo(CO)(PhC=CPh)2(η5-C5Me5)] [BF4] reacts with 3 equiv of CNBut to yield the mixed alkyne - isocyanide complex [Mo(CNBut)3(PhC≡CPh)(??5-C5 Me5)][BF4], 1. Reaction of 1 with a fourth equivalent of CNBut generates [Mo{=C(NHBut)C(Ph)=C(Ph)CN}(CNBut)2(η5 -C5Me5)] [BF4], 2, containing an η3-vinylcarbene ligand formed from the coupling of two of the coordinated isocyanide ligands with the diphenylacetylene, with concomitant protonation of one of these isocyanide fragments and dealkylation of the other. Complex 2 may be deprotonated to give [Mo{C(=NBut)C(Ph)=C(Ph)CN}(CNBut)2(η5 -C5Me5)], 3. Protonation of 1 with HBF4·Et5O generates [Mo{=C(Ph)C(Ph)C=NHBut}(CNBut)2(η5 C5Me5)][BF4]2, 4, by inducing the coupling of a protonated isocyanide ligand with diphenylacetylene, and 4 reacts with CNBut to give 2. A similar reaction of 4 with P(OMe)3 generates [Mo{=C(NHBut)C(Ph)=C(Ph)CN}(CNBut){P(OMe)3}( η5-C5Me5)][BF4], 5, involving the same coupling and elimination pattern. The diphenylacetylene and CNBut ligands of 1 may also be reductively coupled. Thus, treatment of 1 with sodium-mercury amalgam and subsequent protonation with HBF4-Et2O gives the metallacyclopentatriene-like [Mo{=C(NHBut)C(Ph)=C(Ph)C(NHBut)}(CNBut)(η 5-C5Me5)][BF4], 6, or [Mo{=C(NHBut)C(Ph)C(Ph)CH-NHBut}(CNBut)(η 5C5Me5)][BF4], 7, depending upon the solvent. Complex 7 contains an N-protonated η4monoazadiene ligand with a pendant carbene functionality that is also coordinated to the metal. The crystal structures of 1, 2, 3, 6, and 7 have been determined.
