Solution-state interactions of Bis(pentamethylcyclopentadienyl)ytterbium, Cp{sub 2}Yb, with trialkylphosphines and R{sub 3}PX complexes (X = O, NR{prime}, CHR{prime})
- Lawrence Berkeley Lab., CA (United States)
The interactions formed between Cp{sup *}{sub 2}Yb (1) and phosphines and R{sub 3}PX derivatives (X = O, NR{prime}, CHR{prime}M) in solution have been investigated using multinuclear ({sup 1}H, {sup 13}C, {sup 31}P, {sup 171}Yb) and variable-temperature NMR spectroscopy. Adducts of 1 with Me{sub 3}PO and Et{sub 3}PNH undergo slow intermolecular exchange in solution at 25{degree}C (NMR time scale); both 1:1 adducts Cp{sup *}{sub 2}Yb(OPMe{sub 3}), 7; Cp{sup *}{sub 2}Yb(HNPEt{sub 3}), 9 and 1:2 adducts Cp{sup *}{sub 2}Yb(OPMe{sub 3}){sub 2}, 8; Cp{sup *}{sub 2}Yb(HNPEt{sub 3}){sub 2}, 10 have been isolated. The spectroscopic properties of two ylide adducts, Cp{sup *}{sub 2}Yb(Me{sub 2}PhPCHSiMe{sub 3}) (12) and Cp{sup *}{sub 2}Yb(Me{sub 2}PhPCH{sub 2}) (13), have also been investigated. Intermolecular exchange can be slowed at low temperature in both cases; in the former complex a second process, resulting in inequivalent Cp{sup *} rings and inequivalent P-bound methyl groups, can also be slowed at lower temperatures. The nature of this process is discussed in detail. The solid-state structure of 12 has been determined. The NMR values for all of the complexes are discussed in detail. In addition, the {sup 171}Yb chemical shifts for 6, 7, and 12 have been measured, via {sup 1}H/{sup 171}Yb indirect detection utilizing long-range J{sub YbH} coupling, and are discussed. 63 refs., 8 figs., 7 tabs.
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 106757
- Journal Information:
- Organometallics, Journal Name: Organometallics Journal Issue: 9 Vol. 14; ISSN ORGND7; ISSN 0276-7333
- Country of Publication:
- United States
- Language:
- English
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