Heterometallic cubane-type clusters containing group 13 and 16 elements*
29 Apr 2012-Pure and Applied Chemistry (International Union of Pure and Applied Chemistry)-Vol. 84, Iss: 11, pp 2233-2241
TL;DR: In this article, the existence of ruthenium-capped cubane geometry has been revealed by a structural and spectro-scopic analysis of cubane-type clusters.
Abstract: Heterometallic cubane-type clusters were synthesized from the reaction of group 6 and 8 metallaboranes using transition-metal carbonyl compounds. Structural and spectro- scopic study revealed the existence of novel "capped-cubane" geometry. In addition, the crys- tal structure of these clusters distinctly confirms the presence of boride unit as one of the vertices. These clusters possess 60 cluster valence electrons (cve) and six metal-metal bonds. A plausible pathway for the formation of ruthenium-capped cubane has been described.
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TL;DR: In this paper, a half century of research in borane, carborane, and metallaborane chemistry are used to illustrate the often intricate interplay between unexpected findings and targeted synthesis.
26 citations
TL;DR: In this article, the synthesis of group 9 triple-decker-sandwich metallaheteroboranes containing four-membered open B2E2 central rings (E = S or Se) is described.
Abstract: The synthesis of group 9 triple-decker-sandwich metallaheteroboranes containing four-membered open B2E2 central rings (E = S or Se) is described. Further, the reactivity of these molecules with group 8 metal–carbonyl compounds is carried out, yielding closo-polyhedral metallaheteroboranes.
17 citations
TL;DR: In this article, the boron atom is placed in a semi-interstitial position of a M4-butterfly geometry in a 50-cluster valence electron (cve) hetero-metallic boride cluster.
8 citations
TL;DR: In this paper, the authors showed that diphenyl dichalcogenides with an insitu generated intermediate can yield new tungsten-heteroborane compounds with a capped octahedral geometry that is unique due to the presence of three bridging hydrogens in a closo cluster.
2 citations
TL;DR: In this article , the first Se analogue of trishomocubane has been isolated as a 1,2,3-isomer, and the first vertex-fused cluster has been constructed.
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TL;DR: The skeletal structures of carboranes, the higher boranes and borane anions, and many transition-metal carbonyl cluster species are related to the number of skeletal bonding electron-pairs they contain this article.
Abstract: The skeletal structures of carboranes, the higher boranes and borane anions, and many transition-metal carbonyl cluster species are related to the number of skeletal bonding electron-pairs they contain; species with n skeletal atoms adopt closo-structures if held together by (n+ 1) pairs, nido-structures if held together by (n+ 2) pairs, and arachno-structures if held together by (n+ 3) pairs of skeletal bonding electrons.
701 citations
29 Nov 1996
TL;DR: In this paper, the synthesis, X-ray structures, and reactivity of transition metal sulfur complexes are discussed, and a review of synthetic analogs to nitrogenase and other transition metal enzymes relevant to industrial desulfurization is provided.
Abstract: This volume provides an overview of sulfur-coordinated transition metal complexes. It explores how studies of transition metal sulfur sites facilitate understanding of enzymatic and industrial catalytic systems, and it reviews recent research on synthetic analogs to nitrogenase and other transition metal sulfur enzymes relevant to industrial desulfurication. The volume examines synthesis, X-ray structures, and reactivity of transition metal sulfur complexes.
229 citations
"Heterometallic cubane-type clusters..." refers background in this paper
...Cubane-type sulfido clusters have been comprehensively investigated [2], in contrast the corresponding selenido derivatives have received little interest, the only structurally characterized examples being the Mo, Sn, and Pd derivatives with [M3M'Se4] single cube structure [39]....
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Book•
01 Jan 2007TL;DR: In this article, the main group-transition metal clusters and transition metal fragments have been studied in the context of organometallic chemistry and the transition to the solid state from molecules to extended solids.
Abstract: Preface. 1. Introduction 2. Main group clusters - geometric and electronic structure 3. Transition metal clusters - geometric and electronic structure 4. Isoglobal relationships between main group and transition metal fragments - connections to organometallic chemistry 5. Main group-transition metal clusters 6. Transition to the solid state 7. From molecules to extended solids 8. Interconversion of clusters and solid state materials Appendix. Fundamental concepts - a concise review: 1. Elements 2. Atomic properties 3. Homoatomic substances 4. Heteroatomic substances Index.
95 citations
"Heterometallic cubane-type clusters..." refers background in this paper
...Although the qualitative shape of the cubane clusters, shown in Chart 1 and Table 2, remain the same, the M–M distances reflect changes in cluster electronic structure accompanying the addition and loss of electrons [50]....
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TL;DR: All these new metallaboranes have been characterized by mass, (1)H, (11)B, and (13)C NMR spectroscopy and elemental analysis and the structural types were established unequivocally by crystallographic analysis of 1-4.
Abstract: Reaction of (CpnMCl4x) (M = V: n = x = 2; M= Nb: n = 1, x = 0) or (Cp*TaCl4 )( Cp= h 5 -C5H5 ,C p*= h 5 - C5Me5), with (LiBH4·thf) at 708C fol- lowed by thermolysis at 858C in the presence of (BH3·thf) yielded the hy- drogen-rich metallaboranes ((CpM)2- A2H6)2 )( 1 :M = V; 2 :M = Nb) and ((Cp*Ta)2A2H6)2 )( 3) in modest to high yields. Complexes 1 and 3 are the first structurally characterized com- pounds with a metal-metal bond bridg- ed by two hexahydroborate (B2H6) groups forming a symmetrical complex. Addition of (BH3·thf) to 3 results in formation of a metallaborane ((Cp*Ta)2B4H8Am-BH4)) (4) containing a tetrahydroborate ligand, (BH4) , bound exo to the bicapped tetrahedral cage ((Cp*Ta)2B4H8) by two Ta-H-B bridge bonds. The interesting structural feature of 4 is the coordination of the bridging tetrahydroborate group, which has two BH bonds coordinated to the tantalum atoms. All these new metalla- boranes have been characterized by mass, 1 H, 11 B, and 13 C NMR spectrosco- py and elemental analysis and the structural types were established un- equivocally by crystallographic analysis of 1-4.
81 citations
TL;DR: In this paper, the structural relationships between the solid-state compounds consisting of discrete triangular building blocks and their molecular analogues provide an interesting opportunity to study solidstate properties based on the cluster units in molecular clusters.
Abstract: Publisher Summary This chapter discusses group 6 metal chalcogenide cluster complexes and their relationships to solid-state cluster compounds. The cluster complexes of the group 6 metals (molybdenum in particular) are very important because of their relationships to higher-dimensional systems such as the superconducting Chevrel phases and bioclusters such as nitrogenase. Because of the discovery of the Chevrel phase compounds their unique and aesthetically pleasing structures have attracted the attention of many inorganic chemists. The structural relationships between the solid-state compounds consisting of discrete triangular building blocks and their molecular analogues provide an interesting opportunity to study solid-state properties based on the cluster units in molecular clusters. In addition, molecular cluster complexes can be starting materials for preparing the corresponding solid-state cluster compounds by their rational condensation. As molybdenum Chevrel compounds are thermodynamically stable phases, it would be worth trying to prepare the same compounds by low temperature methods using molecular cluster compounds with Mo 6 E 8 cores to gain an insight into the preparation of chromium or tungsten Chevrels by precursor methods.
59 citations