Oxidation - Reduction and Photochemical Reactions of Metalladecaborane Clusters: The Interconversion ofhypercloso-[(η6-C6Me6)RuB9H9] andcloso-[(η6-C6Me6)RuB9H9]2−

Abstract

The most common structure for a 10-vertex polyhedral cluster with a 2n2 skeletal electron count (where n is the number of vertices) is the bicapped square antiprism (I; Scheme 1). [1] In one of the two known isomeric forms of these least one constituent of the product has a limited solubility in it. Under our reaction conditions, indium metal (m.p. 1578C) is indeed molten and dissolves less than 0.001 atomic % nitrogen. [13] The most obvious characteristics of the VLS [12] and SLS [5,6] mechanismsÐone-dimensional fiber or whisker growth morphologies and attached metal-catalyst particlesÐ were clearly evident in the InN samples produced. Consequently, all the key indicators of the SLS growth mechanism were present.The SLS growth process has been previously demonstrated for group III element phosphides and arsenides, [5,6] which are thermally stable at conventional growth temperatures. However, indium nitride is not. The SLS mechanism operates at very low temperatures in comparison to conventional materials-synthesis methods, presumably because it is catalytic and lowers energy barriers for both precursor decomposition and the interfacial steps required for nonmolecular crystal growth (crystal lattice assembly). SLS synthesis of other thermally unstable compounds and crystal structures should be possible. Experimental SectionCompounds tBu 3 In [14] and iPr 3 In [15] were prepared according to the literature. The synthesis of tBu 2 InN 3 (1 b) is described here; iPr 2 InN 3 (1 a) was prepared similarly. MeOH (225 mL, 0.178 g, 5.55 mmol) was added to a dry, O 2 -free solution of tBu 3 In (1.61 g, 5.63 mmol) in hexane (20 mL) at 258C. The mixture was stirred for 10 min and then N 3 SiMe 3 (0.800 mL, 0.660 g, 5.73 mmol) was added, instantly generating a fine white precipitate. The slurry was stirred for 2 h. Precursor 1 b was then collected by filtration and washed with 2 Â 5 mL of hexane (yield: 1.39 g, 5.12 mmol, 91 %).

An Iridaborane Reaction Cycle Driven by PMe3 and BH3⋅THF: Synthesis and Characterization of [Cp*IrB3H7(PMe3)] and [Cp*IrB2H6(PMe3)]

“…The importance of such systems has provided much of the impetus for research in organometallic chemistry 10. 11 Even though significant examples exist,12–14 polyhedral boron chemistry shows a marked lack of reaction cycles either catalytic or stoichiometric. Herein we report a novel stoichiometric cycle in which the iridaboranes, [1‐(Cp*)‐1‐(H) 2 ‐ arachno ‐1‐IrB 3 H 7 ] ( 1 )15 and [1‐(Cp*)‐1‐H‐ arachno ‐1‐IrB 4 H 9 ] ( 2 )15 (Cp*=η 5 ‐C 5 Me 5 ) are interconverted via novel phosphane‐substituted derivatives (Scheme ).…”

Geometry and chemical bonding in polyhedral boranes, metallaboranes, and dimetallaboranes: From closo to isocloso to oblatocloso polyhedra

“…3) [29]. The neutral compound (g 6 -Me 6 C 6 )RuB 9 H 9 has the 20 skeletal electrons for a ten-vertex isocloso structure with the ruthenium atom at the unique degree 6 vertex.…”

14‐Vertex Heteroboranes with 14 Skeletal Electron Pairs: An Experimental and Computational Study

“…Although MO calculations by Mingos and co‐workers support the hypercloso view and the fact that Spencer et al. have shown that the simple addition of two electrons to [ hypercloso ‐(η‐C 6 Me 6 )RuB 9 H 9 ] converts it into [ closo ‐(η‐C 6 Me 6 )RuB 9 H 9 ] 2− , the isocloso descriptor is still in use in the present day …”