Thermal and photochemical carbon-hydrogen bond reactions of alkenes in (tris(pyrazolyl)borato)iridium(I) complexes (original) (raw)

1989, Inorganic Chemistry

resultant products 8, IO, and 12, with the exception of 8f and 8i (see above), were not isolated and were characterized on the basis of 3'P N M R data (see Table V). EHMO calculation^"+^^ were carried out on the simplified complexes (OC),Mo(r-PH2)2Pt(PH,) US), (CO),MO(~-PH~)ZMO(CO), U6), and cis-(COLMo(PH2), (17) with interatomic distances based on X-rav I _crystal structure determination~'~*~ with idealized geometries: C , fo; 15, D2h for 16, and C2, for 17. The P-H distances were 1.40 8, and LMPH = 1 IOo for the PH3 group, and LHPH = 109O for PHI groups. Variation of LHPH from 109 to 120' did not significantly change the observed trends. Values for H,, and orbital exponents were taken from ref 47.. The formyl complex [(OC),(HCO)MO(PH,)~P~(PH,)I-was calculated with C-H = 0.95 A, C=O = 1.33 A, and LMoCH = 117'. The CHO group was rotated around the Mo-C vector in order to find the minimum energy configuration. Acknowledgment. We thank the Natural Sciences and Engineering Research Council of Canada for financial support of this work. Supplementary Material Available: Tables SI-SIV, containing final atomic and thermal parameters of the hydrogen atoms, general temperature factor expressions, bond distances, and bond angles (5 pages); Table SV, containing observed and calculated final structure factors (27 pages). Ordering information is given on any current masthead page.