Reactivity of Triruthenium Furyne and Thiophyne Clusters: Multiple Additions of Thiolato and Selenolato Ligands through Oxidative Addition of S鈥揌 and Se鈥揌 Bonds
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- 作者：Md. Iqbal Hossain ; Md. Delwar H. Sikder ; Shishir Ghosh ; Shariff E. Kabir ; Graeme Hogarth ; Luca Salassa
- 刊名：Organometallics
- 出版年：2012
- 出版时间：April 9, 2012
- 年：2012
- 卷：31
- 期：7
- 页码：2546-2558
- 全文大小：694K
- 年卷期：v.31,no.7(April 9, 2012)
- ISSN：1520-6041
文摘
Reactions of 50-electron furyne and thiophyne clusters Ru3(CO)7(渭-H)(渭3-畏2-C4H2E){渭-P(C4H3E)2}(渭-dppm) (1, 2; E = O, S) with thiols, dithiols, and benzeneselenol leads to the oxidative addition of the E鈥揌 bonds followed by concomitant elimination of the alkyne (probably as the alkene) to afford a range of new thiolato and selenolato triruthenium complexes. Addition of PhSH or iPrSH in boiling benzene affords the 48-electron clusters Ru3(CO)5(渭-SR)2{渭-P(C4H3E)2}(渭-dppm)(渭-H) (3鈥?b>6; E = O, S; R = Ph, iPr) resulting from the addition of 2 equiv of thiol. In contrast, analogous reactions with 1,2-ethanedithiol and 1,3-propanedithiol yield the 50-electron clusters Ru3(CO)3{渭-S(CH2)nS)2{渭-P(C4H3E)2}(渭-dppm)(渭-H) (7鈥?b>10; E = O, S; n = 2, 3), in which four S鈥揌 bonds have been activated. A similar multiple addition reaction is seen upon addition of PhSeH to 1, affording the tetraselenolato complexes Ru3(CO)4(魏1-SePh)(渭-SePh)3{渭-P(C4H3O)2}(渭-dppm)(渭-H) (11) and Ru3(CO)3(渭-SePh)4{渭-P(C4H3O)2}(渭-dppm)(渭-H) (12). Reaction of 2 with PhSeH gave the tetraselenolato complex Ru3(CO)4(魏1-SePh)(渭-SePh)3{渭-P(C4H3S)2}(渭-dppm)(渭-H) (13) together with bis(seleno)-capped Ru3(CO)5{PPh(C4H3S)2}(渭3-Se)2(渭-SePh)2(渭-dppm) (14) resulting from further cleavage of two selenium鈥揷arbon bonds and formation of a new carbon鈥損hosphorus bond. The new clusters have been characterized by a combination of analytical and spectroscopic methods, and the molecular structures of 3, 4, 7, 8, and 11 have been determined by single-crystal X-ray diffraction studies. Complexes 7鈥?b>10 are examples of 50-electron clusters containing three apparent metal鈥搈etal bonds; however, DFT calculations carried out for 7 show that the longest metal鈥搈etal interaction of 3.119 脜 is actually held in place by the bridging thiolato and diphosphine ligands and does not represent a direct metal鈥搈etal bonding interaction.