Competitive Ligand Exchange and Dissociation in Ru Indenyl Complexes
- Roman G. BelliRoman G. BelliDepartment of Chemistry, University of Victoria, P. O. Box 1700, STN CSC, Victoria, British Columbia V8W 2Y2, CanadaMore by Roman G. Belli
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- Yang WuYang WuDepartment of Chemistry, University of Victoria, P. O. Box 1700, STN CSC, Victoria, British Columbia V8W 2Y2, CanadaMore by Yang Wu
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- Hyewon JiHyewon JiDepartment of Chemistry, University of Victoria, P. O. Box 1700, STN CSC, Victoria, British Columbia V8W 2Y2, CanadaMore by Hyewon Ji
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- Anuj JoshiAnuj JoshiDepartment of Chemistry, University of Victoria, P. O. Box 1700, STN CSC, Victoria, British Columbia V8W 2Y2, CanadaMore by Anuj Joshi
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- Lars P. E. YunkerLars P. E. YunkerDepartment of Chemistry, University of Victoria, P. O. Box 1700, STN CSC, Victoria, British Columbia V8W 2Y2, CanadaMore by Lars P. E. Yunker
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- J. Scott McIndoe*J. Scott McIndoe*E-mail: [email protected] (J.S.M.).Department of Chemistry, University of Victoria, P. O. Box 1700, STN CSC, Victoria, British Columbia V8W 2Y2, CanadaMore by J. Scott McIndoe
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- Lisa Rosenberg*Lisa Rosenberg*E-mail: [email protected] (L.R.).Department of Chemistry, University of Victoria, P. O. Box 1700, STN CSC, Victoria, British Columbia V8W 2Y2, CanadaMore by Lisa Rosenberg
Abstract
Kinetic profiles obtained from monitoring the solution-phase substitution chemistry of [Ru(η5-indenyl)(NCPh)(PPh3)2]+ (1) by both electrospray ionization mass spectrometry and 31P{1H} NMR are essentially identical, despite an enormous difference in sample concentrations for these complementary techniques. These studies demonstrate dissociative substitution of the NCPh ligand in 1. Competition experiments using different secondary phosphine reagents provide a ranking of phosphine donor abilities at this relatively crowded half-sandwich complex: PEt2H > PPh2H ≫ PCy2H. The impact of steric congestion at Ru is evident also in reactions of 1 with tertiary phosphines; initial substitution products [Ru(η5-indenyl)(PR3)(PPh3)2]+ rapidly lose PPh3, enabling competitive re-coordination of NCPh. Further solution experiments, relevant to the use of 1 in catalytic hydrophosphination, show that PPh2H out-competes PPh2CH2CH2CO2But (the product of hydrophosphination of tert-butyl acrylate by PPh2H) for coordination to Ru, even in the presence of a 10-fold excess of the tertiary phosphine. Additional information on relative phosphine binding strengths was obtained from gas-phase MS/MS experiments, including collision-induced dissociation experiments on the mixed phosphine complexes [Ru(η5-indenyl)PP′P″]+, which ultimately appear in solution during the secondary phosphine competition experiments. Unexpectedly, unsaturated complexes [Ru(η5-indenyl)(PR2H)(PPh3)]+, generated in the gas-phase, undergo preferential loss of PR2H. We propose that competing orthometallation of PPh3 is responsible for the surprising stability of the [Ru(η5-indenyl)(PPh3)]+ fragment under these conditions.
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