Chemistry on the Rhodacarborane Cluster [9,9-(PPh3)-nido-9,7,8-RhC2B8H11]: Formation of Bidentate Phosphine and Bimetallic Derivatives

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Title:Chemistry on the Rhodacarborane Cluster [9,9-(PPh3)-nido-9,7,8-RhC2B8H11]: Formation of Bidentate Phosphine and Bimetallic Derivatives
Creators:
Volkov, Oleg
Rath, Nigam P.
Barton, Lawrence
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 67, 6, pp. 769-782
Uncontrolled Keywords:Bidentate ligands, NMR <sup>1</sup>H, <sup>11</sup>B, <sup>31</sup>P, Crystal structures, Metallacarboranes, Rhodium, Carboranes, Ruthenium

Abstract

The electronically unsaturated rhodacarborane [9,9-(PPh<sub>3</sub>)<sub>2</sub>-<i>nido</i>-9,7,8-RhC<sub>2</sub>B<sub>8</sub>H<sub>11</sub>] (<strong>1</strong>), reacts with Ph<sub>2</sub>PCH<sub>2</sub>PPh<sub>2</sub> (dppm) to afford [9,9-(dppm-κ<sup>2</sup><i>P</i>)-9-(dppm-κ<i>P</i>)-<i>nido</i>-9,7,8-RhC<sub>2</sub>B<sub>8</sub>H<sub>11</sub>] (<strong>3</strong>), in which the Rh-bonded PPh<sub>3</sub> ligands have been replaced by two dppm ligands, one in a bidentate mode and the second in a unidentate mode with a free PPh<sub>2</sub> end. The structure of <strong>3</strong> is similar to the related, and isoelectronic, species [8,8-(dppm-κ<sup>2</sup><i>P</i>)-8-(dppm-κ<i>P</i>)-<i>nido</i>-8,7-RhSB<sub>9</sub>H<sub>10</sub>] (<strong>4</strong>), but with a difference in the orientation of the ligands. Reaction of <strong>1</strong> with Ph<sub>2</sub>P(CH<sub>2</sub>)<sub>2</sub>PPh<sub>2</sub> (dppe) affords a species tentatively identified as [9,9-(dppe-κ<sup>2</sup><i>P</i>)-9-(dppe-κ<i>P</i>)-<i>nido</i>-9,7,8-RhC<sub>2</sub>B<sub>8</sub>H<sub>11</sub>] (<strong>5</strong>). If allowed to react with [Ru(η<sup>6</sup>-<i>p</i>-cym)Cl<sub>2</sub>]<sub>2,</sub> (<strong>3</strong>) affords [9,9-{Ru(η<sup>6</sup>-<i>p</i>-cym)dppm-κ<sup>2</sup><i>P</i>-(μ-Cl)<sub>2</sub>}-<i>nido</i>-9,7,8-RhC<sub>2</sub>B<sub>8</sub>H<sub>11</sub>] (<strong>6</strong>) containing the group [(μ-Cl)<sub>2</sub>Ru(η<sup>6</sup>-<i>p</i>-cym)dppm] that coordinates in a multidentate mode to Rh. Compounds <strong>3</strong> and <strong>6</strong> are characterized by <sup>11</sup>B, <sup>1</sup>H and <sup>31</sup>P NMR spectroscopy, elemental analysis and X-ray structure determinations. <p>

Title:Chemistry on the Rhodacarborane Cluster [9,9-(PPh3)-nido-9,7,8-RhC2B8H11]: Formation of Bidentate Phosphine and Bimetallic Derivatives
Creators:
Volkov, Oleg
Rath, Nigam P.
Barton, Lawrence
Uncontrolled Keywords:Bidentate ligands, NMR <sup>1</sup>H, <sup>11</sup>B, <sup>31</sup>P, Crystal structures, Metallacarboranes, Rhodium, Carboranes, Ruthenium
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:67
Number:6
Page Range:pp. 769-782
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20020769UNSPECIFIED
ID Code:1953
Item Type:Article
Deposited On:06 Feb 2009 17:14
Last Modified:06 Feb 2009 16:14

Citation

Volkov, Oleg; Rath, Nigam P.; Barton, Lawrence (2002) Chemistry on the Rhodacarborane Cluster [9,9-(PPh3)-nido-9,7,8-RhC2B8H11]: Formation of Bidentate Phosphine and Bimetallic Derivatives. Collection of Czechoslovak Chemical Communications, 67 (6). pp. 769-782. ISSN 0010-0765

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