First‐Row Transition‐Metal–Diborane and –Borylene Complexes |
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| Authors: | Dudekula Sharmila Bijan Mondal Rongala Ramalakshmi Sangita Kundu Dr Babu Varghese Prof Sundargopal Ghosh |
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| Institution: | 1. Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036 (India), Fax: (+91)?44 2257 4202;2. Sophisticated Analytical Instruments Facility, Indian Institute of Technology Madras, Chennai 600036 (India) |
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| Abstract: | A combined experimental and quantum chemical study of Group 7 borane, trimetallic triply bridged borylene and boride complexes has been undertaken. Treatment of {Cp*CoCl}2] (Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) with LiBH4 ? thf at ?78 °C, followed by room‐temperature reaction with three equivalents of Mn2(CO)10] yielded a manganese hexahydridodiborate compound {(OC)4Mn}(η6‐B2H6){Mn(CO)3}2(μ‐H)] ( 1 ) and a triply bridged borylene complex (μ3‐BH)(Cp*Co)2(μ‐CO)(μ‐H)2MnH(CO)3] ( 2 ). In a similar fashion, Re2(CO)10] generated (μ3‐BH)(Cp*Co)2(μ‐CO)(μ‐H)2ReH(CO)3] ( 3 ) and (μ3‐BH)(Cp*Co)2(μ‐CO)2(μ‐H)Co(CO)3] ( 4 ) in modest yields. In contrast, Ru3(CO)12] under similar reaction conditions yielded a heterometallic semi‐interstitial boride cluster (Cp*Co)(μ‐H)3Ru3(CO)9B] ( 5 ). The solid‐state X‐ray structure of compound 1 shows a significantly shorter boron–boron bond length. The detailed spectroscopic data of 1 and the unusual structural and bonding features have been described. All the complexes have been characterized by using 1H, 11B, 13C NMR spectroscopy, mass spectrometry, and X‐ray diffraction analysis. The DFT computations were used to shed light on the bonding and electronic structures of these new compounds. The study reveals a dominant B?H?Mn, a weak B?B?Mn interaction, and an enhanced B?B bonding in 1 . |
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| Keywords: | boranes cobalt density functional calculations manganese X‐ray diffraction |
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