Crystal Engineering of Gold(I) Thiolate Based Compounds via Cooperative Aurophilic and Hydrogen-Bonding Interactions

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• 作者：Biing-Chiau Tzeng ; Annette Schier ; and Hubert Schmidbaur
• 刊名：Inorganic Chemistry
• 出版年：1999
• 出版时间：September 6, 1999
• 年：1999
• 卷：38
• 期：18
• 页码：3978 - 3984
• 全文大小：164K
• 年卷期：v.38,no.18(September 6, 1999)
• ISSN：1520-510X

文摘

Treatment of sodium 2-amino-5-mercapto-1,3,4-thiadiazolate (NaSSNH₂) with monophosphines (triphenylphosphineand trimethylphosphine) and diphosphines [bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), and trans-1,2-bis(diphenylphosphino)ethene (dppee)] affords a series of gold(I) thiolates with therespective stabilizing phosphine ligands [Au(PR₃)(SSNH₂)] (R = Ph 1 and Me 2) and [PP(Au(SSNH₂))₂] (PP =dppm 3, dppe 4 and dppee 5). The crystal structures of the complexes have been determined by single-crystalX-ray diffraction studies, confirming hydrogen-bonded frameworks in the crystal lattices based on the functionsof the SSNH₂ ligands. The triphenylphosphine complex 1 (with crystal diethyl ether, 1·0.5Et₂O) forms a dimersolely via bifurcated hydrogen bonds. In the presence of crystal methanol (1·MeOH) it gives rise to a one-dimensional ladder structure via intermolecular hydrogen-bonding interactions with molecules of crystal methanolas bridges. With a reduced steric effect of the auxiliary ligand, the trimethylphosphine analogue 2 forms a noveltwo-dimensional sheet structure via cooperative intermolecular aurophilic [Au(I)···Au(I) 3.0581(6) Å] and hydrogen-bonding interactions. The bis(diphenylphosphino)methane complex 3·2DMF features dinuclear units associatedinto a meandering chain structure via intramolecular aurophilic and intermolecular hydrogen bonding interactions.Further aggregation is terminated by hydrogen-bonding to crystal solvent molecules. 4·0.5MeOH forms acomplicated network via cooperative intermolecular aurophilic [Au(I)···Au(I) 3.0675(7) Å] and hydrogen-bondinginteractions. With DMF as a chain-terminating solvent molecule, the trans-1,2-bis(diphenylphosphino)ethylenecomplex 5·4DMF can only form isolated dinuclear units hydrogen bonded to these solvent molecules. Complexes2 and 4 are rare examples of two-dimensional frameworks built on cooperative intermolecular aurophilic andhydrogen-bonding interactions in the solid state.