Heterodimetallaboranes of Group 4 and 9 Metals: Analogues of Pentaborane(11) and Hexaborane(12). Issue 38 (8th May 2017)

• Record Type: Journal Article
• Authors: Roy, Dipak Kumar; De, Anangsha; Prakash, Rini; Barik, Subrat Kumar; Ghosh, Sundargopal
• Other Names: Bregadze Vladimir I. guestEditor.; Xie Zuowei guestEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 38/39(2017)
• Page Start: 4452
• Page End: 4458
• Publication Date: 2017-05-08
• Subjects: Zirconium -- Hafnium -- Iridium -- Rhodium -- Boranes; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201700330
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Several early–late heterodimetallaborane clusters have been isolated and structurally characterized through spectroscopic and crystallographic analysis. The thermolysis of [Cp2 Zr(BH4 )2 ] (Cp = η 5 ‐C5 H5 ) with [Cp*IrB3 H9 ] (Cp* = η 5 ‐C5 Me5 ) and [(Cp*Rh)2 B2 H6 ] yielded arachno ‐[(Cp2 Zr)(Cp*Ir)B3 H9 ] (2 ) and arachno ‐[(Cp2 Zr)(Cp*Rh)B4 H10 ] (4 ), respectively. In a similar fashion, the reaction of [Cp2 Hf(BH4 )2 ] was performed with the same set of group 9 metallaboranes that led to the formation of arachno ‐[(Cp2 Hf)(Cp*M′)B4 H10 ] (5 : M′ = Ir;6 : M′ = Rh). To the best of our knowledge, 2 is the first structurally characterized pentaborane(11) analogue containing zirconium, while the clusters5 and6 are the first examples with Hf in a hexaborane(12) core. The bonding between the Zr atoms and the boron ring was studied computationally by DFT methods, and2 can be defined as a dimetallic analogue of arachno ‐B5 H11 on the basis of the combined experimental and computational results. Abstract : We present a series of heterometallaborane analogues of pentaborane(11) and hexaborane(12) incorporating metals from the two ends of the d‐block. These compounds were prepared by the borane condensation method, which enables us to include hafnium in a hexaborane(12) system.