Yang Eric S, Combey Emma, Goicoechea Jose M
Department of Chemistry, University of Oxford, Chemistry Research Laboratory 12 Mansfield Rd. Oxford OX1 3TA UK.
Department of Chemistry, Indiana University 800 East Kirkwood Ave. Bloomington Indiana 47405 USA
Chem Sci. 2023 Apr 6;14(17):4627-4632. doi: 10.1039/d3sc01126g. eCollection 2023 May 3.
The synthesis of group 9 pyridine-diimine complexes M(PDI)X and [M(PDI)L] (M = Co, Rh; PDI = 1,1'-(pyridine-2,6-diyl)bis(-(2,6-diisopropylphenyl)ethan-1-imine); X = CP, CCH; L = CO, BuNC) bearing a series of strong-field ligands, including the cyaphide ion (C[triple bond, length as m-dash]P), is reported. A combined experimental and computational comparative study of the group 9 PDI cyaphide complexes Co(PDI)(CP) and Rh(PDI)(CP), as well as the N-heterocyclic carbene (NHC) gold(i) cyaphide complex Au(IDipp)(CP) (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene), reveals the σ donor and π acceptor properties of the κ-cyaphido ligand, and allow us to suggest a position for this ion in the spectrochemical series.
报道了一系列含强场配体（包括氰基负离子（C≡P））的第9族吡啶二亚胺配合物M(PDI)X和[M(PDI)L]（M = Co、Rh；PDI = 1,1'-（吡啶-2,6-二基）双（-（2,6-二异丙基苯基）乙-1-亚胺）；X = CP、CCH；L = CO、BuNC）的合成。对第9族PDI氰基配合物Co(PDI)(CP)和Rh(PDI)(CP)以及N-杂环卡宾（NHC）金（I）氰基配合物Au(IDipp)(CP)（IDipp = 1,3-双（2,6-二异丙基苯基）咪唑-2-亚基）进行的实验与计算相结合的对比研究，揭示了κ-氰基配体的σ给体和π受体性质，并使我们能够在光谱化学序列中为该离子确定一个位置。
