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Title: Stereodynamics of trans-((t-Bu) sub 2 PPh) sub 2 MCl sub 2 (M = Pt(II) and Pd(II)) and trans-((t-Bu) sub 2 PPh) sub 2 M(CO)Cl (M = Rh(I) and Ir(I)). Dynamic NMR and X-ray crystallographic studies

Journal Article · · Journal of Physical Chemistry; (USA)
DOI:https://doi.org/10.1021/j100379a020· OSTI ID:6190420

Single-crystal X-ray analysis of trans-((t-Bu){sub 2}PPh){sub 2}MCl{sub 2} for which M = Pt(II) or Pd(II) reveals a molecular conformation (C{sub i}) in which both phenyl groups are mutually anti. In both cases, the metal atom lies on a crystallographic inversion center and the overall geometry at the metal template is essentially square planar. The {sup 31}P({sup 1}H) dynamic NMR (DNMR) spectra of both trans-((t-Bu){sub 2}PPh){sub 2}PdCl{sub 2} and trans-((t-Bu){sub 2}PPh){sub 2}PtCl{sub 2} show a decoalescence at low temperature into four singlets (four diastereomeric conformations). One singlet resonance is strongly dominant in both complexes. Two singlets correspond to the two diastereomeric conformations in which the phenyl groups are anti to each other and oriented on the same side or opposite sides of the coordination plane (C{sub i} and C{sub 2} molecular symmetry). The other two singlets are assigned to diastereomeric conformations in which the phenyl groups are mutually syn and on the same side or opposite sides of the coordination plane (C{sub s} and C{sub 2} molecular symmetry).

OSTI ID:
6190420
Journal Information:
Journal of Physical Chemistry; (USA), Vol. 94:16; ISSN 0022-3654
Country of Publication:
United States
Language:
English