High-Spin Organocobalt(II) Complexes in a Thioether Coordination Environment

详细信息    查看全文

• 作者：Julie A. DuPont ; Michael B. Coxey ; Peter J. Schebler ; Christopher D. Incarvito ; William G. Dougherty ; Glenn P. A. Yap ; Arnold L. Rheingold ; Charles G. Riordan
• 刊名：Organometallics
• 出版年：2007
• 出版时间：February 12, 2007
• 年：2007
• 卷：26
• 期：4
• 页码：971 - 979
• 全文大小：167K
• 年卷期：v.26,no.4(February 12, 2007)
• ISSN：1520-6041

文摘

A series of electronically and coordinatively unsaturated four-coordinate organocobalt(II) complexes,[PhTt^tBu]Co(R) ([PhTt^tBu] = phenyltris((tert-butylthio)methyl)borate; R = Me, Et, Ph, Bn) have beenprepared by reaction of [PhTt^tBu]CoCl with the corresponding R₂Mg reagent. These high-spin, S = 3/2,complexes have been characterized spectroscopically and several of their structures determined by X-raydiffraction. The R = allyl derivative, [PhTt^tBu]Co(ages/gifchars/eta.gif" BORDER=0 >³-allyl), is low spin. Reaction of [PhTt^tBu]Co(R) withCO yielded the acyl adducts [PhTt^tBu]Co(CO)C(O)R when R = Me, Et, Ph. These five-coordinate, low-spin complexes possess square pyramidal stereochemistry with a thioether occupying the apical position.In contrast, [PhTt^tBu]Co(R), R = Bn or allyl, reacted with CO generating the brown cobalt(I) dicarbonyl[PhTt^tBu]Co(CO)₂. The latter reaction is proposed to proceed via CO-promoted Co-C bond homolysis.The Ni complex [ages/gifchars/kappa.gif" BORDER=0 >²-PhTt^tBu]Ni(ages/gifchars/eta.gif" BORDER=0 >³-allyl) shows no reactivity with CO under similar conditions. Each ofthe [PhTt^tBu]Co(R) species reacts with NO, generating brown [ages/gifchars/kappa.gif" BORDER=0 >²-PhTt^tBu]Co(NO)₂ in good yield.