1977
DOI: 10.1139/v77-031
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Chemistry of metal hydrides. Part XIX. Stereochemical changes at platinum during the insertion of acetylenes with platinum(II) hydrides

Abstract: The reactions of trans-[PtH(PEt3)2(acetone)]+ and trans-[PtH(PEt3)2(CO)]+ with a variety of acetylenes are described. The geometries of the products with respect to the platinum centre and to the stereochemistry of the alkenyl group have been determined on the basis of their 1H nmr parameters. For reactions with the cation containing acetone, and particularly from a variable temperature 1H nmr study of its reaction with 2-butyne in the presence of water, the insertion pathway is shown to be entirely analogous … Show more

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Cited by 17 publications
(3 citation statements)
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“…However, theoretical calculations indicate that the low energy pathway for alkyne insertions in platinum(II) systems proceeds from four-coordinate square-planar complexes . There is much experimental evidence to substantiate this prediction. ,,, In addition, as mentioned above, we have not obtained any evidence for the associative attack of diphenylacetylene on 1 or any 4-coordinate intermediate in this system. Thus, we disfavor an associative mechanism for the conversion of 12 to 8 .…”
Section: Discussionmentioning
confidence: 57%
See 1 more Smart Citation
“…However, theoretical calculations indicate that the low energy pathway for alkyne insertions in platinum(II) systems proceeds from four-coordinate square-planar complexes . There is much experimental evidence to substantiate this prediction. ,,, In addition, as mentioned above, we have not obtained any evidence for the associative attack of diphenylacetylene on 1 or any 4-coordinate intermediate in this system. Thus, we disfavor an associative mechanism for the conversion of 12 to 8 .…”
Section: Discussionmentioning
confidence: 57%
“…Each Pt is essentially square-planar coordinate in which the two σ-bound carbons are oriented cis to one another and each is trans to a coordinated π-bond. The stereochemistry about the terminal double bond of the tetraphenylbutadienyl ligand is trans.
4 ORTEP drawing of one of the two independent molecules in the asymmetric unit of 8 .
…”
Section: Resultsmentioning
confidence: 99%
“…The starting material frares-L2PtHCl was prepared by Parshall's method;18 and the following metal acetylides [14][15][16][17][18][19][20][21][22] were prepared by literature methods: trons-L2Pt(C=CR)2 (14 and 15 (R = H or Me));19 (j7-C6H5)(OC)2Fe(C=CPh) (16);20 LAu(C=CPh) (17 and 18 (L = PEt, or PPhg));21•22 (s-C6H5)(OC)3W(C^CPh) (19);23 tr<ms-L2Ni(C=CPh)2 (20);24 and trons-L2Pd(C=CPh)2 (21). 26 Preparation of [ 2(µ-0=€ ß)(0^3 ß)( 3)4] 6 (5).…”
Section: Methodsmentioning
confidence: 99%