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Diplatinum A‐frame complexes with a bridging (di)boron unit in the apex position were synthesized in a single step by the double oxidative addition of dihalo(di)borane precursors at a bis(diphosphine)‐bridged Pt\(^{0}\)\(_{2}\) complex. While structurally analogous to well‐known μ‐borylene complexes, in which delocalized dative three‐center‐two‐electron M‐B‐M bonding prevails, theoretical investigations into the nature of Pt−B bonding in these A‐frame complexes show them to be rare dimetalla(di)boranes displaying two electron‐sharing Pt−B σ‐bonds. This is experimentally reflected in the low kinetic stability of these compounds, which are prone to loss of the (di)boron bridgehead unit.
In the molecular structure of the dinuclear title compound \([η^5-(C_5(CH_3)_5)(CO)Fe{(μ-BCl)(μ-CO)}PtCl(P(C_6H_{11})_3)]·C_6H_6\), the two metal atoms, iron(II) and platinum(II), are bridged by one carbonyl (μ-CO) and one chloridoborylene ligand (μ-BCl). The \(Pt^{II}\) atom is additionally bound to a chloride ligand situated trans to the bridging borylene, and a tricyclohexylphosphane ligand \((PCy_3)\) trans to the carbonyl ligand, forming a distorted square-planar structural motif at the \(Pt^{II}\) atom. The \(Fe_{II}\) atom is bound to a pentamethylcyclopentadienyl ligand \([η^5-C_5(CH_3)_5]\) and one carbonyl ligand (CO), forming a piano-stool structure. Additionally, one benzene solvent molecule is incorporated into the crystal structure, positioned staggered relative to the pentamethylcyclopentadienyl ligand at the \(Fe^{II}\) atom, with a centroid–centroid separation of 3.630 (2) Å.