Interactions of cis-P{sub 2}PtX{sub 2} complexes (X = H, CH{sub 3}) with bis(pentamethylcyclopentadienyl)ytterbium
Journal Article
·
· Journal of the American Chemical Society
- Univ. of California, Berkeley, CA (United States)
The interactions formed in solution between the bent lanthanide metallocene Cp{sup *}{sub 2}Yb (1) and cis-P{sub 2}PtX{sub 2} complexes (P{sub 2} = a chelating phosphine; X = H, CH{sub 3}) have been investigated using NMR spectroscopy. We have found that 1 forms interactions of significant strength with cis dihydride complexes of platinum(II). The nature of this interaction is not affected by a change in the P-Pt-P bite angle, a somewhat surprising result. While intermolecular exchange can be stopped only at very low temperature for the dimethyl platinum derivative 9, the solid-state structure of this adduct shows a rare agostic bonding mode for the bridging methyl groups. The methyl hydride derivative, 11, undergoes slow exchange in solution at 25{degree}C and, in contrast to 9, shows a Pt-C-Yb bonding mode in the solid state. The solution-state Yb-methyl interaction likely arises mainly as a result of the strong Yb-hydride interaction holding the Yb center near the methyl group (i.e., it results from conformational constraints) and appears to involve both Yb-C and C-H- -Yb interactions, although the exact nature of this interaction cannot be unequivocally determined from the solution-state data. 63 refs., 9 figs., 10 tabs.
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 70339
- Journal Information:
- Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 22 Vol. 117; ISSN JACSAT; ISSN 0002-7863
- Country of Publication:
- United States
- Language:
- English
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