Coordinatively Unsaturated Semisandwich Complexes of Ruthenium with Phosphinoamine Ligands and Related Species: A Complex Containing (R,R)-1,2-Bis((diisopropylphosphino)amino)cyclohexane
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- 作者：M. Dolores Palacios ; M. Carmen Puerta ; Pedro Valerga ; Agustí ; Lledó ; s ; Edouard Veilly
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：August 20, 2007
- 年：2007
- 卷：46
- 期：17
- 页码：6958 - 6967
- 全文大小：253K
- 年卷期：v.46,no.17(August 20, 2007)
- ISSN：1520-510X
文摘
The syntheses of the chloro complexes [Ru(
rs/eta.gif" BORDER=0 >5-C5R5)Cl(L)] (R = H, Me; L = phosphinoamine ligand) (1a-d) havebeen carried out by reaction of [(rs/eta.gif" BORDER=0 >5-C5H5)RuCl(PPh3)2] or {(rs/eta.gif" BORDER=0 >5-C5Me5)RuCl}4 with the corresponding phosphinoamine(R,R)-1,2-bis((diisopropylphosphino)amino)cyclohexane), R,R-dippach, or 1,2-bis(((diisopropylphosphino)amino)ethane),dippae. The chloride abstraction reactions from these compounds lead to different products depending on thestarting chlorocomplex and the reaction conditions. Under argon atmosphere, chloride abstraction from [(rs/eta.gif" BORDER=0 >5-C5Me5)RuCl(R,R-dippach)] with NaBAr'4 yields the compound [(rs/eta.gif" BORDER=0 >5-C5Me5)Ru(rs/kappa.gif" BORDER=0 >3P,P'-(R,R)-dippach)][BAr'4] (2b) which exhibitsa three-membered ring Ru-N-P by a new coordination form of this phosphinoamine. However, under the sameconditions the reaction starting from [(rs/eta.gif" BORDER=0 >5-C5Me5)RuCl(dippae)] yields the unsaturated 16 electron complex [(rs/eta.gif" BORDER=0 >5-C5Me5)Ru(dippae)][BAr'4] (2d). The bonding modes of R,R-dippach and dippae ligands have been analyzed byDFT calculations. The possibility of tridentate P,N,P-coordination of the phosphinoamide ligand to a fragment [(rs/eta.gif" BORDER=0 >5-C5Me5)Ru]+ is always present, but only the presence of a cyclohexane unit in the ligand framework converts thisbonding mode in a more favorable option than the usual P,P-coordination. Dinitrogen [(rs/eta.gif" BORDER=0 >5-C5R5)Ru(N2)(L)][BAr'4](3a-d) and dioxygen complexes [(rs/eta.gif" BORDER=0 >5-C5H5)Ru(O2)(R,R-dippach)][BPh4] (4a) and [(rs/eta.gif" BORDER=0 >5-C5Me5)Ru(O2)(L)][BPh4] (4b,d)have been prepared by chloride abstraction under dinitrogen or dioxygen atmosphere, respectively. The presenceof 16 electron [(rs/eta.gif" BORDER=0 >5-C5H5)Ru(R,R-dippach)]+ species in fluorobenzene solutions of the corresponding dinitrogen ordioxygen complexes in conjunction with the presence of [BAr'4]- gave in some cases a small fraction of [Ru(rs/eta.gif" BORDER=0 >5-C5H5)(rs/eta.gif" BORDER=0 >6-C6H5F)][BAr'4] (5a), which has been isolated and characterized by X-ray diffraction.
rs/eta.gif" BORDER=0 >5-C5R5)Cl(L)] (R = H, Me; L = phosphinoamine ligand) (1a-d) havebeen carried out by reaction of [(rs/eta.gif" BORDER=0 >5-C5H5)RuCl(PPh3)2] or {(rs/eta.gif" BORDER=0 >5-C5Me5)RuCl}4 with the corresponding phosphinoamine(R,R)-1,2-bis((diisopropylphosphino)amino)cyclohexane), R,R-dippach, or 1,2-bis(((diisopropylphosphino)amino)ethane),dippae. The chloride abstraction reactions from these compounds lead to different products depending on thestarting chlorocomplex and the reaction conditions. Under argon atmosphere, chloride abstraction from [(rs/eta.gif" BORDER=0 >5-C5Me5)RuCl(R,R-dippach)] with NaBAr'4 yields the compound [(rs/eta.gif" BORDER=0 >5-C5Me5)Ru(rs/kappa.gif" BORDER=0 >3P,P'-(R,R)-dippach)][BAr'4] (2b) which exhibitsa three-membered ring Ru-N-P by a new coordination form of this phosphinoamine. However, under the sameconditions the reaction starting from [(rs/eta.gif" BORDER=0 >5-C5Me5)RuCl(dippae)] yields the unsaturated 16 electron complex [(rs/eta.gif" BORDER=0 >5-C5Me5)Ru(dippae)][BAr'4] (2d). The bonding modes of R,R-dippach and dippae ligands have been analyzed byDFT calculations. The possibility of tridentate P,N,P-coordination of the phosphinoamide ligand to a fragment [(rs/eta.gif" BORDER=0 >5-C5Me5)Ru]+ is always present, but only the presence of a cyclohexane unit in the ligand framework converts thisbonding mode in a more favorable option than the usual P,P-coordination. Dinitrogen [(rs/eta.gif" BORDER=0 >5-C5R5)Ru(N2)(L)][BAr'4](3a-d) and dioxygen complexes [(rs/eta.gif" BORDER=0 >5-C5H5)Ru(O2)(R,R-dippach)][BPh4] (4a) and [(rs/eta.gif" BORDER=0 >5-C5Me5)Ru(O2)(L)][BPh4] (4b,d)have been prepared by chloride abstraction under dinitrogen or dioxygen atmosphere, respectively. The presenceof 16 electron [(rs/eta.gif" BORDER=0 >5-C5H5)Ru(R,R-dippach)]+ species in fluorobenzene solutions of the corresponding dinitrogen ordioxygen complexes in conjunction with the presence of [BAr'4]- gave in some cases a small fraction of [Ru(rs/eta.gif" BORDER=0 >5-C5H5)(rs/eta.gif" BORDER=0 >6-C6H5F)][BAr'4] (5a), which has been isolated and characterized by X-ray diffraction.