Trimetallaborides as starting points for the syntheses of large metal-rich molecular borides and clusters

Treatment of an anionic dimanganaborylene complex with cationic coinage metal complexes led to the coordination of the incoming metal and displacement of dimethylsulfide in the formation of hexametalladiborides.

The crystal data of 3 were collected on a Bruker X8-Apex II diffractometer with a CCD area detector and multi-layer mirror monochromated Mo K radiation. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included in structure factors calculations. All hydrogen atoms were assigned to idealised geometric positions.  The crystal data of 4 were collected on a Bruker X8-Apex II diffractometer with a CCD area detector and multi-layer mirror monochromated Mo K radiation. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included in structure factors calculations. All hydrogen atoms were assigned to idealised geometric positions.
The displacement parameters of the fragments CuPCy 3 and PtPCy 3 were constrained to the same value.
The Uii displacement parameters of the fragments CuPCy 3 and PtPCy 3 were restrained with ISOR keyword to approximate isotropic behavior.
Crystal data for 4: C 50 H 76 BCuMn 2 O 4 P 2 Pt, M r = 1182.37, red block, 0.24×0.18×0.11 mm 3 , Triclinic space group P-1, a = 11.1740 (8)   The crystal data of 7 were collected on a Bruker X8APEX diffractometer with a CCD area detector and multi-layer mirror monochromated Mo K radiation. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were included in structure factors calculations. All hydrogen atoms were assigned to idealised geometric positions.

Computational Details:
For the investigation of potential closed shell interactions, geometry optimization was carried out using the Amsterdam Density Functional (ADF) 8 program at the OLYP/TZP. 9 All calculations were conducted within the zeroth-order regular approximation (ZORA) formalism. 10 To obtain the singlet state, spin-restricted calculations were performed constraining the projection of the total electronic spin along a reference axis to 0. Frequency calculations were conducted to determine if each stationary point corresponds to a minimum. Reported bond orders are of the Mayer bond order type 11 and atomic charges were determined according to the Hirshfeld charge analysis. 12 Dispersion was included via the addition of the D3 version of Grimme's dispersion with Becke-Johnson damping. 13 The Jmol 14 program and the Graphical User Interface (ADF-GUI) -a part of the ADF package, were used for visualization purposes.
For the reported thermochemistry, calculations were performed in the Gaussian 09 software suite. 15 For compound 2 and its related thermochemistry, optimizations were carried out at the B3LYP/6-311+G(d,p) level of theory for all atoms and checked via frequency calculation to ensure the stationary point was a true minimum with no imaginary frequencies. The calculated electronic and free energies at 298.15 K are given in Table 1. For compound 3, small atoms were calculated at the B3LYP/6-311+G(d,p) level, while Au and Mn were treated at with the LANL2DZ pseudopotential.
After a complete conversion, indicated by the emergence of a 11 B NMR signal at 208 ppm, the solution was filtered and stored at -35 °C. Slow crystallization led to the isolation of red crystals of 2 suitable for X-ray diffraction. For (2) (14) Cu1-C 1.920 (5)