Bulky Amidinate Complexes of Indium(III). Synthesis and Structure of [CyNC(^tBu)NCy]₂InCl

Abstract

Reaction of 2 equiv of lithium dicyclohexylacetamidinate with InCl(3) affords the new species In[CyNC(Me)NCy](2)Cl (Cy = cyclohexyl) (1). Compound 1 reacts with MeLi to yield In[CyNC(Me)NCy](2)CH(3) (2) and also reacts with a third equivalent of amidinate to yield In[CyNC(Me)NCy](3) (3). Two new bulky amidinate ligands are prepared by the addition of (t)BuLi to CyN=C=NCy and Me(3)SiN=C=CSiMe(3), respectively. Subsequent reactions with InCl(3) lead to the high-yield syntheses of In[CyNC(CMe(3))NCy](2)Cl (4) and [Me(3)SiN(CMe(3))NSiMe(3)](2)InCl (5). Spectroscopic and elemental analyses confirm the formulas of all of these new species. Compound 4 is further characterized by X-ray crystallography and shown to possess a distorted trigonal bipyramidal coordination geometry around the metal center with the chloride group in the equatorial position. Crystal data for 4: triclinic, P&onemacr;, a = 12.545(7) Å, b = 13.482(8) Å, c = 11.965(6) Å, alpha = 102.08(5) degrees, beta = 92.00(5) degrees, gamma = 64.36(4) degrees, Z = 2, R = 0.029, R(w) = 0.045.

Aluminum and Indium Complexes derived from Guanidines, Triazenes, and Amidines

“…Both 12 and 13 exhibit distorted trigonal bipyramidal coordination arrangements, with the HFxy ligands ( 12 ), or the extended Fet In–N contact nitrogen and the HFet In–N nitrogen ( 13 ), occupying the apical positions [ trans angles 12 175.54(7)°, 13 143.97(16)°, sum of equatorial angles 12 359.02°, 13 330.19°]. The In–Cl bonds of 12 [2.4066(7), 2.3676(7) Å] and 13 [2.3872(14), 2.3900(14) Å] are longer than that of [InCl(Fiso) 2 ] [2.3574(11) Å],10c but consistent with that of [InCl(CyNC( t Bu)NCy) 2 ] [2.405(4) Å, Cy = c ‐C 6 H 11 ] 26…”

Use of diagnostic neutral losses for structural information on unknown aromatic metabolites: an experimental and theoretical study

“…The hydride ligand was located from difference maps and refined isotropically; the InH bond length is 1.71(6) Å (av 1.68 Å in [InH 3 (PCy 3 )], C y =cyclohexyl4). The geometry of 1 is similar to that of the related indium chloride complex, [InCl{CyNC( t Bu)NCy} 2 ],14 and the only other example of a structurally characterized amidinate Group 13 hydride complex, [AlH{(Me 3 Si)NC(Ph)N(SiMe 3 )} 2 ],15 though the bulk of the Ar substituents in 1 cause it to be significantly more distorted. We believe that these groups also lead to the remarkable thermal stability of the complex by forming a heavily protected “pocket” in which the hydride ligand sits (Figure 1 b).…”

Kinetic Control over the Thermal Stability of the InH Bond: Synthesis and Characterization of Amido Indium Hydride Complexes

“…The hydride ligand was located from difference maps and refined isotropically; the In À H bond length is 1.71(6) (av 1.68 in [InH 3 (PCy 3 )], Cy = cyclohexyl [4] ). The geometry of 1 is similar to that of the related indium chloride complex, [InCl{CyNC(tBu)NCy} 2 ], [14] and the only other example of a structurally characterized amidinate Group 13 hydride complex, [AlH{(Me 3 -Si)NC(Ph)N(SiMe 3 )} 2 ], [15] though the bulk of the Ar substituents in 1 cause it to be significantly more distorted. We believe that these groups also lead to the remarkable thermal stability of the complex by forming a heavily protected "pocket" in which the hydride ligand sits (Figure 1 b).…”