A New Strategy for the Preparation of Metallaboranes − Solvothermal Synthesis and Structural Characterisation of Two Nido 11‐vertex Diplatinaundecaborane Clusters

Abstract

Two novel nido 11‐vertex diplatinaundecaborane clusters [(μ‐PPh2)(PPh3)2Pt2B9H6Cl(OiPr)2] (1) and [(μ‐PPh2)(PPh3)2Pt2B9H6(OiPr)3] (2) have been solvothermally synthesised and characterised by elemental analysis, IR, Raman, 1H and 13C NMR spectroscopy and single‐crystal X‐ray diffraction. The latter analysis revealed that two Pt atoms remain in neighbouring positions of the open Pt2B3 face in both clusters which were markedly different from the products obtained from the identical starting mixture under refluxing conditions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

Synthesis and characterization of three nickel(ii) carborane complexes containing nido- or closo-carborane diphosphine ligand

“…To compare the outcome obtained from different conditions and further understand the degradation of the closo diphosphine ligand 1,2-(PPh 2 ) 2 -1,2-C 2 B 10 H 10 , three reactions were investigated under two different environments. In addition, enlightened by the result reported by our group that the solvothermal method could be employed to synthesize metallaborane [14], we have also successfully introduced this method into the reaction of the carborane. These results will be discussed in this paper, together with description of the molecular structures of three different carborane Ni complexes obtained from the different reaction environments with the formula [Ni 2 (l-Cl (2) and [NiBr 2 {1,2-(PPh 2 ) 2 -1,2-C 2 B 10 H 10 }] AE CH 2 Cl 2 (3).…”

“…The result obtained from the reaction of anhydrous NiCl 2 with the closo diphosphine is same to the above reaction, indicating that the existing H 2 O has no influence on the reaction itself. As our group previously reported that solvothermal method can be employed to synthesize metallaborane [14]. Here we tentatively introduced this method into the reaction of carborane.…”

Polyhedral Dipalladaborane Chemistry. The Molecular Structure and Cluster Electron Count of [7,8-(PPh3)2-7,8-(μ-PPh2)-9,11-(OEt)2-nido-7,8-Pd2B9H8]

“…These are in principle close analogues of the present dipalladium species [(PPh 3 ) 2 (µ-PPh 2 )Pd 2 B 9 H 8 (OEt) 2 ] (1), except that each of the reported formulations for compounds 4-7 implies one cluster electron fewer than for compound 1. In the reports of compounds 4 to 7 the location of cluster hydrogen atoms is not addressed, and no cluster 11 B and 1 H NMR data are presented [17][18][19] . The formulations [(PPh 3 ) 2 (µ-PPh 2 )Pt 2 B 9 H 6 (OEt) 3 ], [(PPh 3 ) 2 (µ-PPh 2 )-Pt 2 B 9 H 6 X-(O iso Pr) 2 ] (X = H, Cl) and [(PPh 3 ) 2 (µ-PPh 2 )Pt 2 B 9 H 6 (O iso Pr) 3 ] imply paramagnetic odd-electron species, which in turn may imply intense UV/VIS absorptions, but in the reports on 4, 5, 6 and 7 their colours were not recorded.…”

Novel 11-Vertex, 11-Skeletal Electron Pair Tantalaborane of Unusual Shape

“…They are [(Cp*Re) 2 B 9 H 9 ], 11 I, [exo-BH 2 (Cp*M) 2 B 9 H 14 ] (M = Ru, Re), 10b II, and [(μ-PPh 2 )(PPh 3 ) 2 Pt 2 B 9 H 6 Cl(OiPr) 2 ] or [(μ-PPh 2 )(PPh 3 ) 2 Pt 2 B 9 H 6 (OiPr) 3 ], III. 12 The observed geometry of I is different from that of the canonical deltahedra of [B 11 H 11 ] 2À ; however this can be related to the canonical ones by diamondÀsquareÀdiamond (dsd) rearrangements. 13 The isostructural metallaborane type II with an exopolyhedral BH 2 can be generated from a 13-vertex docosahedron by removal of two vertices of connectivity five and six.…”

“…The diplatinaundecarborane cluster type III, on the other hand, exhibits a nido 11-vertex {Pt 2 B 9 } polyhedral skeleton with two Pt atoms in neighboring positions of the open Pt 2 B 3 face. 12 The molecular structure of these compounds reveal that they have different geometries despite having the same number of borane fragments. Cluster 2 may thus be considered as the next member of this series containing a M 2 B 9 framework.…”