Alkynylcarbyne complexes containing various tri- and bidentate ligands such as cyclopentadienide,tris(pyrazolyl)borate,bis(pyrazolyl)acetate and tmeda: synthesis and spectroscopic properties |
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| Institution: | 1. College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450052, PR China;2. Henan Academy of Arts and Crafts, Zhengzhou 450008, PR China;1. Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Ferrara, Via Luigi Borsari, 46, 44121 Ferrara, Italy;2. Centro di Strutturistica Diffrattometrica, Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Ferrara, Via Luigi Borsari, 46, 44121 Ferrara, Italy;1. Key Lab of Polyoxometallate Science, Department of Chemistry, Northeast Normal University, Changchun 130024, People’s Republic of China;2. College of Chemistry and Chemical Engineering, Qufu Normal University, Qufu 273165, People’s Republic of China;3. College of Chemistry and Chemical Engineering, Xinxiang University, Xinxiang, Henan 453003, People’s Republic of China;4. Department of Chemistry and Pharmaceutical Engineering, Suihua University, Suihua 152061, People’s Republic of China;1. School of Chemistry, University of KwaZulu-Natal, Private Bag X01, Pietermaritzburg 3209, South Africa;2. Department of Chemistry, University of Oxford, Chemistry Research Laboratory, South Parks Road, Oxford OX1 3TA, UK;3. Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK;4. Department of Materials, Imperial College London, Royal School of Mines, Exhibition Road, London SW7 2AZ, UK |
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| Abstract: | The (alkynylcarbyne)tungsten complexes L3(CO)2WCCCR] (3a,b–6a,b) L3=hydrotris(3,5-dimethylpyrazol-1-yl)]borato (Tp′, 3), hydrotris(pyrazol-1-yl)]borato (Tp, 4), cyclopentadienyl (Cp, 5), bis(3,5-dimethylpyrazol-1-yl)acetato (bdmpza, 6); R=SiMe3 (a), Ph (b)] were prepared in a stepwise fashion from W(CO)6] and LiCCR], (CF3CO)2O and ML3] (M=Na, K). The formation of 6a,b was highly selective, only complexes with a trans arrangement of the carboxylate group of bdmpza and the alkynylcarbyne ligand were detected. The reaction of W(CO)6] with LiCCR], C2O2Cl2 and tmeda afforded trans-Cl(CO)2(tmeda)WCCCR] (7a,b). The electron-donating potential of the different tripodal ligands L3 was studied by IR- and 13C-NMR spectroscopy and compared to that of the ligand combination Cl/tmeda. The IR data suggest that in these complexes bdmpza is a weaker electron donor than Tp′ and Tp but displays stronger electron-donating abilities than Cp. The structures of 6b and 7b were established by X-ray structural analyses. |
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