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论文类型：期刊论文

发表时间：2016-03-14

发表刊物：ORGANOMETALLICS

收录刊物：SCIE、EI

卷号：35

期号：5

页面范围：751-757

ISSN号：0276-7333

摘要：By employing S(CH2CH2S )(2) (tpdt) and O(CH2CH2S )(2) (opdt) as bridging ligands, two nickeliron and two nickelruthenium heterodimetallic complexes, [Cp*M(-1(3)SSS?:2(2)SS-tpdt)Ni(dppe)][PF6] (1, M = Fe; 3, M = Ru) and [Cp*M(-1 kappa(SSO)-S-3:2 kappa(SS)-S-2-opdt)Ni(dppe)][PF6] (2, M = Fe; 4, M = Ru) (Cp* = eta(5)-C5Me5; dppe = Ph2P(CH2)(2)PPh2), were obtained by a one-pot synthetic method and were identified by spectroscopy and X-ray crystallography. At 1 atm of CO, the pendant oxygen atom dissociated from the iron or ruthenium center and rapidly transferred to the nickel center when a CO molecule attacked the iron or ruthenium center in 2 and 4. However, there was no similar reaction occurring in 1 and 3 with the pendant sulfur atom. We confirmed the solid-state structure of the CO complex [Cp*Fe(t-CO)(mu-1 kappa(SS)-S-2:2 kappa(SSO)-S-3-opdt)Ni(dppe)][PF6] (5), which represents a possible configuration in the CO-inhibited state of [NiFe]-hydrogenase and exhibits no catalytic activity in electrochemical proton reduction.