Mass spectrometry-directed synthesis of ‘early–late’ sulfide-bridged heterobimetallic complexes from the metalloligand [Pt2(PPh3)4(µ-S)2] and oxo compounds of vanadium(v), molybdenum(vi) and uranium(vi)

Abstract

Surprising nucleophilic reactions of the metalloligand [Pt 2 (PPh 3) 4 (-S) 2 ] with metavanadate and molybdate ions, and uranyl nitrate, monitored using electrospray ionisation mass spectrometry (ESMS), reveals new and facile synthetic routes to the 'earlylate' heterobimetallic complexes [Pt 2 (PPh 3) 4 ( 3-S) 2 VO(OMe) 2 ] + , [Pt 2 (PPh 3) 4 ( 3-S) 2 MoO 2 (OMe)] + , and [Pt 2 (PPh 3) 4 ( 3-S) 2 UO 2 ( 2-NO 3) 2 ], the first example of a sulfidebridged platinum-uranium complex.

Extending The Reaction Landscape of the {Pt(μ‐S)2Pt} Core: From Metal Centers to Non‐Metallic Electrophiles

“…At the same time, the wide coordination environments offered by main group or transition metals together with the nature of their accompanying LЈ species, either ligands or counter ions, enhance the structural diversity of this family of derivatives. As depicted in Scheme 8, aggregates of known structure include those with varied coordination geometries about the heterometal: linear, [41,42] angular, [43] T-shaped, [42,44] Y-shaped, [45] tetrahedral, [12,15,46] square planar, [12,47] square pyramidal, [48] distorted trigonal prismatic, [49] trigonal bipyramidal, [50] hexagonal bipyramidal, [51] ''piano stool'' [52] and others. [53,54] These aggregates also display the ability of the [L 2 Pt(µ-S) 2 PtL 2 ] metalloligand to function as a unidentate, [41] bridging, [53] or chelating ligand.…”

Coordination chemistry of the metalloligand [Pt2(μ-S)2(PPh3)4] with nickel(II) complexes – an electrospray mass spectrometry directed synthetic study

“…We have successfully used electrospray mass spectrometry to probe the reactivity of 4 NiL] 2+ are confirmed [7] when L is a neutral bidentate phosphine ligand (such as dppf) or 2,2'-bipyridine. In these cases, the reduced lability results in retention of this ligand in preference to an anion.…”

“…In this paper we report the application of this methodology to the study of the reactivity of [Pt 2 (-S) 2 (PPh 3 ) 4 ] 1 towards a range of nickel(II) complexes. Little work has been done to date in this area; while derivatives of the {Pt 2 S 2 } core are known for many metals, the only nickel species known to date is [Pt 2 (-S) 2 (PPh 3 ) 4 Ni(dppe)] 2+ .…”

“…

SynopsisReactions of [Pt 2 (-S) 2 (PPh 3 ) 4 ] with a range of nickel(II) substrates have been explored using electrospray mass spectrometry, coupled with synthesis and characterization in 2 selected systems. The X-ray crystal structure of [Pt 2 (-S) 2

…”

Alkylation of [Pt2(μ-S)2(PPh3)4] with boronic acid derivatives

“…2 The bridging sulfides are electron-rich and the reactivity towards metal fragments has been exploited in the synthesis of multimetallic aggregates. [3][4][5][6][7][8][9][10][11] Alkylation reactions of 1 with mild electrophiles was realised in the early preliminary studies. [12][13][14][15] Recently, the rudimentary reactivity of 1 with simple mild alkylating agents 13 has been extended to functionalized alkylating agents (electrophiles).…”