Organic Matrix Photochemical Studies of Rhenacarborane Nitrosyl Complexes. Evidence for Linkage Isomeric Nitrosyl Photointermediates
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- 作者：Thomas E. Bitterwolf ; W. Bruce Scallorn ; Callie A. Weiss ; and Paul A. Jelliss
- 刊名：Organometallics
- 出版年：2002
- 出版时间：April 29, 2002
- 年：2002
- 卷：21
- 期：9
- 页码：1856 - 1860
- 全文大小：60K
- 年卷期：v.21,no.9(April 29, 2002)
- ISSN：1520-6041
文摘
The photochemistry of the rhenacarborane nitrosyl compounds [1,2-R2-3,3-(CO)2-3-NO-closo-3,1,2-ReC2B9H9], where R = H, I, and R = Me, II, has been studied in Nujol andmethytetrahydrofuran (MeTHF) frozen glasses at ca. 90 K. Visible light photolysis givesrise to a new species that has been assigned to the isonitrosyl linkage isomer, while ultravioletphotolysis gives rise to a second species believed to be the 
2-NO linkage isomer. In MeTHFhigh-energy photolysis also gives rise to a CO-loss product. Photolysis of derivatives of I,[3-L-3-L'-3-NO-closo-3,1,2-ReC2B9H11], where L = CO, L' = PMe3, III; L = CO, L' = CNC6H3Me2-2, 6, IV, and L = L' = CNC6H3Me2-2,6, V, all give rise to a photoproduct believed to bethe 2-NO lnkage isomer. There was no evidence of the isonitrosyl isomer in these cases.Complexes III and IV also undergo CO loss. Ultraviolet photolysis of [3,3,3-(CO)3-closo-3,1,2-RuC2B9H11], VI, in MeTHF results in CO loss and formation of the corresponding [3,3-(CO)2-3-MeTHF-closo-3,1,2-RuC2B9H11] derivative. In frozen Nujol, ultraviolet photolysis ofVI gives rise to a CO-loss species. Upon visible light back-photolysis or annealing of thesample, this photoproduct gives rise to a second dicarbonyl species of unknown structure.
2-NO linkage isomer. In MeTHFhigh-energy photolysis also gives rise to a CO-loss product. Photolysis of derivatives of I,[3-L-3-L'-3-NO-closo-3,1,2-ReC2B9H11], where L = CO, L' = PMe3, III; L = CO, L' = CNC6H3Me2-2, 6, IV, and L = L' = CNC6H3Me2-2,6, V, all give rise to a photoproduct believed to bethe 2-NO lnkage isomer. There was no evidence of the isonitrosyl isomer in these cases.Complexes III and IV also undergo CO loss. Ultraviolet photolysis of [3,3,3-(CO)3-closo-3,1,2-RuC2B9H11], VI, in MeTHF results in CO loss and formation of the corresponding [3,3-(CO)2-3-MeTHF-closo-3,1,2-RuC2B9H11] derivative. In frozen Nujol, ultraviolet photolysis ofVI gives rise to a CO-loss species. Upon visible light back-photolysis or annealing of thesample, this photoproduct gives rise to a second dicarbonyl species of unknown structure.