# Reactions of Platinum Terminal Polyynyl Complexes trans-(C6F5)(p-tol3P)2Pt(C≡C)nH (n = 2–4) and n-BuLi, Generation of Functional Equivalents of Pt(C≡C)nLi Species, and Derivatization with Organic and Inorganic Electrophiles

## TL;DR

This paper explores chemical reactions involving platinum complexes and various reagents, revealing new ways to form and study these compounds.

## Contribution

The study presents new synthetic methods and structural insights into platinum polyynyl complexes and their derivatives.

## Key findings

- Functional equivalents of deprotonated platinum species were successfully generated and characterized.
- Crystal structures of several platinum and tungsten complexes were determined.
- Hydride complexes were detected in multiple reaction scenarios.

## Abstract

Reactions of the title complexes and n-BuLi (1.5
equiv, –45 °C) afford functional equivalents of the deprotonated
species trans-(C6F5)(p-tol3P)2Pt(C≡C)nLi (n = 2–4), as assayed
by subsequent additions of MeI or Me3SiCl to give trans-(C6F5)(p-tol3P)2Pt(C≡C)nMe
(66–52%) or trans-(C6F5)(p-tol3P)2Pt(C≡C)nSiMe3 (63–49%). However, 31P NMR data suggest more complicated mechanistic scenarios,
and small amounts of the hydride complex trans-(C6F5)(p-tol3P)2PtH (independently synthesized from the chloride complex, AgClO4, and NaBH4) are detected in most cases. Analogous
sequences involving trans-(C6F5)(p-tol3P)2Pt(C≡C)2H and benzyl bromide, D2O, or W(CO)6/Me3O+ BF4– similarly
afford products with Pt(C≡C)2Bn, Pt(C≡C)2D, or Pt(C≡C)2C(OCH3)=W(CO)5 linkages. The crystal structures of the tungsten and corresponding
SiMe3 adduct, the three Pt(C≡C)nMe species, and hydride complex are determined.