Chemistry of N, S‐Heterocyclic Carbene and Metallaboratrane Complexes: A New η3‐BCC‐Borataallyl Complex. Issue 39 (6th August 2015)

• Record Type: Journal Article
• Authors: Roy, Dipak Kumar; De, Anangsha; Panda, Subhankar; Varghese, Babu; Ghosh, Sundargopal
• Is Part Of: Chemistry. Volume 21:Issue 39(2015)
• Page Start: 13732
• Page End: 13738
• Publication Date: 2015-08-06
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201501014
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>A high‐yielding synthetic route for the preparation of group 9 metallaboratrane complexes [Cp*MBH(L)<sub>2</sub>], <bold>1</bold> and <bold>2</bold> (<bold>1</bold>, M=Rh, <bold>2</bold>, M=Ir; L=C<sub>7</sub>H<sub>4</sub>NS<sub>2</sub>) has been developed using [{Cp*MCl<sub>2</sub>}<sub>2</sub>] as precursor. This method also permitted the synthesis of an Rh–N, S‐heterocyclic carbene complex, [(Cp*Rh)(L<sub>2</sub>)(1‐benzothiazol‐2‐ylidene)] (<bold>3</bold>; L=C<sub>7</sub>H<sub>4</sub>NS<sub>2</sub>) in good yield. The reaction of compound <bold>3</bold> with neutral borane reagents led to the isolation of a novel borataallyl complex [Cp*Rh(L)<sub>2</sub>B{CH<sub>2</sub>C(CO<sub>2</sub>Me)}] (<bold>4</bold>; L=C<sub>7</sub>H<sub>4</sub>NS<sub>2</sub>). Compound <bold>4</bold> features a rare η<sup>3</sup>‐interaction between rhodium and the B‐C‐C unit of a vinylborane moiety. Furthermore, with the objective of generating metallaboratranes of other early and late transition metals through a transmetallation approach, reactions of rhoda‐ and irida‐boratrane complexes with metal carbonyl compounds were carried out. Although the objective of isolating such complexes was not achieved, several interesting mixed‐metal complexes [{Cp*Rh}{Re(CO)<sub>3</sub>}(C<sub>7</sub>H<sub>4</sub>NS<sub>2</sub>)<sub>3</sub>] (<bold>5</bold>), [Cp*Rh{Fe<sub>2</sub>(CO)<sub>6</sub>}(μ‐CO)S] (<bold>6</bold>), and [Cp*RhBH(L)<sub>2</sub>W(CO)<sub>5</sub>] (<bold>7</bold>; L=C<sub>7</sub>H<sub>4</sub>NS<sub>2</sub>) have been isolated. All of the new compounds have been characterized in solution by mass spectrometry, IR spectroscopy, and <sup>1</sup>H, <sup>11</sup>B, and <sup>13</sup>C NMR spectroscopies, and the structural types of <bold>4</bold>–<bold>7</bold> have been unequivocally established by crystallographic analysis.</p> </abstract>