Products Cited in Publications Worldwide Gyroscope-like platinum(IV) complexes of the macrocyclic dibridgehead diphosphine P((CH2)14)3P

Gyroscope-like platinum(IV) complexes of the macrocyclic dibridgehead diphosphine P((CH2)14)3P

Zhu, Yun; Dey Baksi, Sourajit; Bhuvanesh, Nattamai; Reibenspies, Joseph H.; Gladysz, John A.

DOI:

Abstract

Reactions of the platinum(II) dihalide complexes trans-Pt(X)2(P((CH2)14)3P)(X = Cl,trans-4;Br,trans-6) and excess X2 give the platinum(IV) tetrahalide complexes trans-Pt(X)4(P((CH2)14)3P)(trans-5,trans-7) in 84-95% yields. Their crystal structures are determined and the PtXn conformations and bond lengths compared to those of trans-4 and trans-6. In one instance, a reaction of trans-PtBr2(P((CH2)14)3P) (trans-6) and MeMgBr (2.4 equiv) gave not the precedented product cis-Pt(Me)2(P((CH2)14)3P), but rather a small amount of the platinum(IV) tetra-Me complex trans-Pt(Me)4(P((CH2)14)3P) (trans-8), as verified crystallog. and by diagnostic NMR signals. Independent syntheses were attempted. Reactions of trans-PtCl4(P((CH2)14)3P) (trans-5) or trans-PtBr4(P((CH2)14)3P) (trans-7) with excesses of common sources of Me- were unsuccessful. Thus, the free dibridgehead diphosphine P((CH2)14)3P, which can incorporate PtX2 (X = Cl or Br) to give trans-PtCl2(P((CH2)14)3P) (trans-4) or trans-PtBr2(P((CH2)14)3P) (trans-6), was treated with the PtMe4 source Pt2Me8(μ-SMe2)2. However, this gave instead isomeric cis-Pt(Me)4(P((CH2)14)3P) (cis-8), and attempts to establish cis/trans equilibrium were unsuccessful.

Keywords

Platinum(IV) ; Dibridgehead diphosphines ; Methyl complexes ; Crystal structures ; Gyroscopes ; PtX 4 rotators

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