Stepwise Conversion of an Osmium Trimethylstannyl Complex to a Triiodostannyl Complex and Nucleophilic Substitution Reactions at the Tin-Iodine Bonds

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• 作者：Alex M. Clark ; Clifton E. F. Rickard ; Warren R. Roper ; Timothy J. Woodman ; and L. James Wright
• 刊名：Organometallics
• 出版年：2000
• 出版时间：May 1, 2000
• 年：2000
• 卷：19
• 期：9
• 页码：1766 - 1774
• 全文大小：144K
• 年卷期：v.19,no.9(May 1, 2000)
• ISSN：1520-6041

文摘

Treatment of the coordinatively unsaturated osmium complex Os(SnMe₃)Cl(CO)(PPh₃)₂with sodium dimethyldithiocarbamate gives the coordinatively saturated complex Os(SnMe₃)(es/gifchars/eta.gif" BORDER=0 >²-S₂CNMe₂)(CO)(PPh₃)₂ (1). Complex 1 reacts with excess SnI₄ to give Os(SnMeI₂)(es/gifchars/eta.gif" BORDER=0 >²-S₂CNMe₂)(CO)(PPh₃)₂ (3) in high yield. A redistribution reaction of 3 with anequimolar amount of 1 provides Os(SnMe₂I)(es/gifchars/eta.gif" BORDER=0 >²-S₂CNMe₂)(CO)(PPh₃)₂ (2). The last remainingmethyl group bonded to tin in 3 is removed by treatment with a slight excess of I₂, givingthe triiodostannyl complex Os(SnI₃)(es/gifchars/eta.gif" BORDER=0 >²-S₂CNMe₂)(CO)(PPh₃)₂ (4). Both 3 and 4 have beenfurther derivatized by replacement of the halide groups on tin. Treatment of 3 withpyridinium tribromide gives Os(SnMeBr₂)(es/gifchars/eta.gif" BORDER=0 >²-S₂CNMe₂)(CO)(PPh₃)₂ (5). Treatment of 3 withcatechol provides Os(SnMe[1,2-O₂C₆H₄])(es/gifchars/eta.gif" BORDER=0 >²-S₂CNMe₂)(CO)(PPh₃)₂ (6), while the similarreaction with 1,2-ethanedithiol gives Os(SnMe[1,2-S₂C₂H₄])(es/gifchars/eta.gif" BORDER=0 >²-S₂CNMe₂)(CO)(PPh₃)₂ (7).Complex 4 undergoes reaction with an excess of KOH to give the trihydroxystannyl complexOs(Sn[OH]₃)(es/gifchars/eta.gif" BORDER=0 >²-S₂CNMe₂)(CO)(PPh₃)₂ (8). Treatment of 4 with triethanolamine gives Os(Sn[OCH₂CH₂]₃N)(es/gifchars/eta.gif" BORDER=0 >²-S₂CNMe₂)(CO)(PPh₃)₂ (9), while reaction with nitrilotriacetic acid givesthe metal-substituted stannatranone Os(Sn[OC(O)CH₂]₃N)(es/gifchars/eta.gif" BORDER=0 >²-S₂CNMe₂)(CO)(PPh₃)₂ (10). Thecrystal structures of 1, 4, 5, 7, and 10 have been determined.