Homogeneous CO Hydrogenation: Ligand Effects on the Lewis Acid ...

Figure S168. 13 C{ 1 H} NMR.
E. Reductions of [(Ph 2P(CH 2) 3B(C 8H 14))Re(<strong>CO</strong>) 5][OTf] ([1-P 1][OTf]).
Reaction of [1-P 1][OTf] with [HPt][PF 6].
A 10 mL scintillation vial was charged with 24.6 mg (0.0299 mmol) [1-P 1][OTf], which was
dissolved in ~0.6 mL C 6D 5Cl. To the stirring solution was added 19.2 mg (0.0299 mmol) [HPt] +
as a solid portionwise. After stirring for a couple minutes, the mixture was transferred to a J-
Young NMR tube, and monitored by 1 H and 31 P{ 1 H} NMR. After 30 minutes, the ratio of
formyl: Re-H was 1.00:0.03. After 1.5 hours, the ratio was 1.00:0.61. After 2.5 hours the ratio
was 1.00:28.68. After 5.5 hours, all of the formyl was consumed. During the course of the
reaction what appeared to be a Re-alkyl (4.72, d, J PH = 6.6 Hz) was present; the small (~10 %)
amount remained constant over the course of the reaction. NMR spectra data for Re-CHO
species: 1 H NMR (C 6D 5Cl, 300 MHz): δ 0.89 (br, 2H, Ph 2PCH 2CH 2CH 2B(C 8H 14)), 1.04 (br, 2H,
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