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DOI: 10.1039/A604808K (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 415-420

Synthesis, isomerism and supramolecular chemistry of diphenylmethanimine complexes of the coinage metals

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Wolfgang Schneider, Andreas Bauer and Hubert Schmidbaur

Abstract

The reactions of [AuCl(SMe2)] or [AuBr(C4H8S)] with 1 equivalent of diphenylmethanimine led to the formation of the complexes [AuCl(Ph2C[double bond, length as m-dash]NH)] 1a, [Au(Ph2C[double bond, length as m-dash]NH)2][AuCl2] 1b and [Au(Ph2C[double bond, length as m-dash]NH)2][AuBr2] 2, respectively. Treatment of 1a, 1b with KI in the two-phase system dichloromethane–water induced a redox process to give Au0 and [Au(Ph2C[double bond, length as m-dash]NH)2][I3] 3. The same result was obtained when AuI and Ph2C[double bond, length as m-dash]NH were allowed to react under anhydrous and oxygen-free conditions. Copper(I) iodide reacted with an excess of Ph2C[double bond, length as m-dash]NH with formation of the complex [CuI(Ph2C[double bond, length as m-dash]NH)] 4. Bis(diphenylmethanimine) complexes of gold, [Au(Ph2C[double bond, length as m-dash]NH)2]BF4 5, and silver, [Ag(Ph2C[double bond, length as m-dash]NH)2]BF4 6, were prepared by the reaction of 2 equivalents of the ketimine and [Au(PhCN)2]BF4 or AgBF4 in dichloromethane or tetrahydrofuran solutions, respectively. The crystal structures of the complexes 1a, 1b, 2, 3, 5 and 6 have been determined. The (Ph2C[double bond, length as m-dash]NH)AuCl units of compound 1a form infinite zigzag chains via weak Au[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]Au contacts [3.3633(5) Å]. In 1b two AuCl2- anions and two (Ph2C[double bond, length as m-dash]NH)2Au+ cations form a tetranuclear Z-type unit with Au[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]Au contacts of 3.1944(5) [Au(1)[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]Au(2)], 3.604(1) [Au(1)[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]Au(2′)] and 3.392(1)Å [Au(1)[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]Au(1 ′)]. The N–H[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]Cl geometry suggests hydrogen bonding between the hydrogen and chlorine atoms of neighbouring ions. The bromine compound 2 is isostructural to the chloride 1b with slightly longer Au[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]·[thin space (1/6-em)]Au distances. Compound 3 shows bis(diphenylmethanimine)gold(I) cations and triiodide anions with no anomalies in the packing and in bond distances and angles. The geometry of the silver(I) and gold(I) complexes 5 and 6 are quite similar except for the observation that the Au–N bond is 0.11 Å shorter than the Ag–N bond, which suggests that two-co-ordinate gold(I) is indeed smaller than two-co-ordinate silver(I) in systems with nitrogen-containing ligands, as previously observed for phosphine complexes.

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