7.3 OBJETIVO 3 Evaluar el potencial de desarrollo de una APP de destinos de naturaleza
7.3.2 Identificación de estrategias comparativas y competitivas
Icosahedral closo-{C2B10} carborane clusters as ligands for transition metals
exhibit rich coordination chemistry with several binding motifs: neutral borane ligands, anionic boryls, and formally dianionic carborynes. The three-dimensional polyhedral
Figure 1.6. Displacement ellipsoid plots (50% probability) of (a) a bimetallic C,B-carboranyl complex (RhCp*)2(2,3-o-C2B10H9)(CSNHPh) (14)137 and (b) a
bimetallic B,B-carboranyl complex (IrCp*)2(μ-Cl)(2,6-C2B10H8)(COO)2
(15).59 Most of the hydrogen atoms have been omitted for clarity. Note the
relatively long B(1)–B(2) bond (1.89(3) Å) and the lack of metal-metal bonding in 15.
15
structure of carboranes allows a combination of some of these bonding modes in one complex; for example, a B–H∙∙∙M bridging interaction vicinal to the B–M boryl group. Furthermore, assembly of multimetallic complexes on the surface of carborane clusters offers a wide flexibility in the number of metal centers and their mutual arrangement and bonding. The stability of B-metalated carboranyls in comparison to other boryl complexes will undoubtedly be one of the key factors in expansion of a number of isolated examples of this class of coordination compounds. The development of synthetic protocols for the formation of metal-boron bonds is still an underexplored area, and some new experimental routes are expected to emerge. The use of carborane clusters as ligands for multiple metal centers may lead to a design of well-defined molecular analogs of borophene-type structures on metallic surfaces.150–152
16
R
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25
C
HAPTER 2P
OBOPP
INCERC
OMPLEXES OFN
ICKEL(II):S
YNTHESIS ANDB
-H
A
CTIVATION OF THEC
ARBORANEL
IGAND UPONO
XIDATION WITHI
ODINE*26 1. Introduction
Nickel complexes have recently attracted significant attention due to their versatile reactivity in catalysis and relevance to “green” chemistry.1-5 Rigid tridentate pincer ligand
frameworks provide a promising balance between stability and reactivity of the complexes. Nickel pincer complexes have been utilized in various catalytic systems, including carbon- carbon and carbon-heteroatom coupling reactions, hydroamination, and other processes.6- 13 In addition to carbon-based pincer backbones, there is a growing number of heteroatom
ligand architectures including nitrogen, silicon, and boron-based pincer complexes.14,15 In
particular, complexes containing metal-boron bonds have attracted attention due to the strong trans-influence of the ligand, the versatility of possible coordination modes, and cooperative metal-ligand reactivity.16-22 For example, nickel-based boryl pincer complexes
have been demonstrated to engage in cooperative dihydrogen activation.23,24
Polyhedral boron clusters have been actively utilized in ligand design due to their unique steric hindrance and unusual electronic properties.25,26 Carborane cages are often
incorporated as a bulky auxiliary group attached to a heteroatom donor in phosphines, amines, and, recently, in heterocyclic carbene systems.27-32 Furthermore, the carboranyl
complexes containing a metal center directly connected to a cage through either C-M or B- M exohedral bonds have been demonstrated to provide even more dramatic steric hindrance and protection in the vicinity of the metal center.33-37 The unique three-
dimensional geometry of icosahedral boron cages enforces a close contact between vicinal B-H bonds of the cage and the exohedral metal center which differentiates carborane-based ligands from planar aryl- or pyridine-based systems.
27
Herein we report the synthesis of the first structurally characterized B-metalated nickel(II) carborane pincer complex and its unusual metal-ligand reactivity upon reaction with molecular iodine.