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Treatment of an anionic dimanganaborylene complex ([{Cp(CO)\(_2\)Mn}\(_2\)B]\(^-\)) with coinage metal cations stabilized by a very weakly coordinating Lewis base (SMe\(_2\)) led to the coordination of the incoming metal and subsequent displacement of dimethylsulfide in the formation of hexametalladiborides featuring planar four-membered M\(_2\)B\(_2\) cores (M = Cu, Au) comparable to transition metal clusters constructed around four-membered rings composed solely of coinage metals. The analogies between compounds consisting of B\(_2\)M\(_2\) units and M\(_4\) (M = Cu, Au) units speak to the often overlooked metalloid nature of boron. Treatment of one of these compounds (M = Cu) with a Lewis-basic metal fragment (Pt(PCy\(_3\))\(_2\)) led to the formation of a tetrametallaboride featuring two manganese, one copper and one platinum atom, all bound to boron in a geometry not yet seen for this kind of compound. Computational examination suggests that this geometry is the result of d\(^{10}\)-d\(^{10}\) dispersion interactions between the copper and platinum fragments.
The title compound, \(C_{19}H_{17}PS_2\), results from the direct deprotonation of diphenylmethylphosphine sulfide and subsequent reaction with diphenyl disulfide. The C-P and C-S bond lengths of 1.8242 (18) and 1.8009 (18) Å, respectively, of the central P-C-S linkage are comparable to those found in the sulfonyl analogue, but are considerably longer than those reported for the dimetallated sulfonyl compound. The dihedral angle between the benzene rings of the diphenylmethyl moiety is 69.46 (7)°. No distinct intermolecular interactions are present in the crystal structure.
C\(_{19}\)H\(_{16}\)N\(_2\)OS, triclinic, P (1) over bar (no. 2), a= 8.1510(3) angstrom, b = 8.8021(3) angstrom, c =11.3953(5) angstrom, alpha =72.546(2)degrees, beta=84.568(2)degrees, gamma =80.760(2)degrees, V =768.86(5) angstrom(3), Z =2, R\(_{gt}\)(F) = 0.0491, WR\(_{ref}\)(F-2) = 0.1494, T =100 K.
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.