Reactions of Elemental Indium and Indium(I) Bromide with Nickel−Bromine Bonds:  Structure of (η⁵-C₅H₅)(Ph₃P)NiInBr₂(OPPh₃)

Abstract

The reactions of elemental indium and In(I)Br with the carbonyl-free organonickel complexes (eta(5)-C(5)H(5))(PR(3))Ni-Br (R = CH(3), C(6)H(5)) have been studied in some detail. Either redox reactions to yield the ionic products [(eta(5)-C(5)H(5))(PR(3))(2)Ni][InBr(4)] (2a,b) occurred or the Ni-In bound systems (eta(5)-C(5)H(5))(PPh(3))Ni-InBr(2)(OPPh(3)) (3a) and [(eta(5)-C(5)H(5))(PPh(3))Ni](2)InBr (4) were obtained in good yields. The new compounds were characterized by elemental analysis, NMR, and mass spectrometry. A short Ni-In bond of 244.65(9) pm was found for 3a. Single crystal data for (eta(5)-C(5)H(5))(PPh(3))Ni-InBr(2)(OPPh(3)).THF (3a): triclinic, P1 with a = 1124.9(3), b = 1353.2(4), c = 1476.4(4) pm, alpha = 94.74(2) degrees, beta = 101.78(2) degrees, gamma = 109.64(1) degrees, V = 2044(1) x 10(6) pm(3), Z = 2, R = 0.053 (R(w) = 0.063).

Transition Metal Chemistry of Low Valent Group 13 Organyls

“…[ [56,57] while only special conditions such as the presence of strong Lewis-bases (e.g. Ph 3 PϭO, quinuclidine) suppress this reaction so that NiϪIn bonded compounds can be isolated.…”

Two Types of Intramolecular Lewis-Base Adducts with the [2-(Dimethylamino)ethyl]cyclopentadienyl Ligand: Synthesis and Crystal Structures of {η5:η1-C5H4[(CH2)2NMe2]}Ni−I and {η5-μ-C5H4[(CH2)2NMe2]}(Me3P)Ni−InI2,

“…In order to achieve this insertion of In I X (X = Cl, Br, I) into the Ni−I bond of 3 , however, the presence of PPh 3 or PMe 3 is necessary (Scheme ). Without this ancillary ligand 3 does not react cleanly with In I X. Interestingly, the related chemistry of Cp(PPh 3 )Ni-Br with In I Br is also very much dependent on the solvent and the presence of Lewis base ligands …”

“…The mixed-metal nickel gallium complex 7 (Scheme ) was prepared by insertion of Ga 2 Cl 4 into the Ni-Ni bond of 2 , but a suitable crystal for X-ray analysis could not be obtained. A homologous mixed-metal nickel indium complex had been derived from 2 by a similar route 13a. Compound 7 sublimed unchanged under moderate conditions (10 -3 Torr, 120 °C).…”

Ni[In{C(SiMe3)3}4]: An Organometallic Nickel-Indium Compound Analogous to [Ni(CO)4]

“…The sum of the covalent radii can be estimated to be about 260 pm. The short Ni ± In bond lengths in complexes such as [Cp(Ph 3 P)Ni ± InBr 2 (OPPh 3 )] (244.6 pm) [16] and [Cp(CO)Ni ± InBr 2 (NC 7 H 13 )] (246.2 pm) [17] have been explained in terms of Ni(dp) ± ligand(s*) interactions. The intramolecular In ± In distances of 377 pm in 2 lie in the range of twice the van der Waals radius of indium (380 pm) and indicate no significant bonding interaction between the In atoms.…”