Insertion of B-X (X = Cl, SMe2) Moieties into Ruthenaborane Frameworks: Synthesis and Characterization of (5-C
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- 作者：Sundargopal Ghosh ; Thomas P. Fehlner ; Alicia M. Beatty ; and Bruce C. Noll
- 刊名：Organometallics
- 出版年：2005
- 出版时间：May 9, 2005
- 年：2005
- 卷：24
- 期：10
- 页码：2473 - 2480
- 全文大小：243K
- 年卷期：v.24,no.10(May 9, 2005)
- ISSN：1520-6041
文摘
The reaction of nido-1,2-(
P>5-C5Me5Ru)2(
-H)2B3H7 (1) with the dichloroborane BHCl2·SMe2results in the formation of three sets of B-Cl inserted metallaborane products: nido-1,2-(5-C5Me5Ru)2(-H)B4H7Cl2 (2), pileo-2,3-(5-C5Me5Ru)2(-H)B4H5Cl2 (three geometric isomers,3-5), and pileo-2,3-(5-C5Me5Ru)2(-H)B4H4Cl3 (a pair of geometric isomers, 6 and 7). Whenthe same reaction was carried out under more forcing conditions, three new metallaboranecompounds, closo-1-(SMe2)-2,3-(5-C5Me5Ru)2(3-H)B5HCl3 (a pair of geometric isomers, 8and 9) and closo-2,3-(5-C5Me5Ru)2B6H3Cl3 (10), were isolated in low yield in addition to2-7. Compounds 8 and 9 exhibit a capped-octahedral geometry, and 10 exhibits a seven-sep (skeletal electron pair) bicapped-octahedral geometry. Reaction of nido-2,4-(5-C5Me5Ru)2B6H12 and nido-2,3-(5-C5Me5Ru)2B8H12 with BHCl2·SMe2 results in substitution ofterminal H by Cl, producing nido-2,4-(5-C5Me5Ru)2B6H10Cl2 (11) and nido-2,3-(5-C5Me5Ru)2B8H11Cl (12) in 82% and 75% yields, respectively.
-H)2B3H7 (1) with the dichloroborane BHCl2·SMe2results in the formation of three sets of B-Cl inserted metallaborane products: nido-1,2-(5-C5Me5Ru)2(-H)B4H7Cl2 (2), pileo-2,3-(5-C5Me5Ru)2(-H)B4H5Cl2 (three geometric isomers,3-5), and pileo-2,3-(5-C5Me5Ru)2(-H)B4H4Cl3 (a pair of geometric isomers, 6 and 7). Whenthe same reaction was carried out under more forcing conditions, three new metallaboranecompounds, closo-1-(SMe2)-2,3-(5-C5Me5Ru)2(3-H)B5HCl3 (a pair of geometric isomers, 8and 9) and closo-2,3-(5-C5Me5Ru)2B6H3Cl3 (10), were isolated in low yield in addition to2-7. Compounds 8 and 9 exhibit a capped-octahedral geometry, and 10 exhibits a seven-sep (skeletal electron pair) bicapped-octahedral geometry. Reaction of nido-2,4-(5-C5Me5Ru)2B6H12 and nido-2,3-(5-C5Me5Ru)2B8H12 with BHCl2·SMe2 results in substitution ofterminal H by Cl, producing nido-2,4-(5-C5Me5Ru)2B6H10Cl2 (11) and nido-2,3-(5-C5Me5Ru)2B8H11Cl (12) in 82% and 75% yields, respectively.