Structural characterization of crystalline tetrakis(2-aminoethanethiol)trinickel(II) chloride, [Ni{Ni(NH2CH2CH2S)2}2]Cl2. New basic trinuclear metal system containing nickel(II)-nickel(II) interactions

Abstract

Ranian and infrared spectra have been obtained for the tetrameric molecules [(CI-Is)3PtX]4 where X = OH, C1, and I. For the hydroxide and chloride, single-crystal Raman polarizations provide unambiguous determination of the symmetry species of the observed frequencies. Assignments to internal coordinates were made by intercomparisons of the spectra and comparisons with related molecules. Of particular interest is the observation in each case of a set of three strong low-frequency bands in the Raman spectrum, with frequency ratios close to those predicted for a tetrahedron of like atoms bound to one another in the "simple cluster" approximation. Normal-coordinate analyses were carried out using force fields containing a force constant for metal-metal interaction. Absolute Raman intensities were measured for the totally symmetric modes and used to calculate bond polarizability derivatives and estimate bond orders. The results indicate that bonds between the platinum atoms and the bridging X atoms are weak and highly ionic. The Raman intensities provide evidence for weak interaction between platinum atoms, which decreases with increasing internuclear distance along the series X = OH, C1, and I. The force constants for Pt-Pt stretching decrease in the same order but are much larger than expected in relation to the weakness of the Pt-Pt interaction. The bonding pattern is siniilar to that found previously for the oxygen-bridged complexes Bis(OH)126+, Pb4(0H)d4+, and T14(0C2Hj)a.

The preparation, characterization, and crystal and molecular structure of oxobis(ethan-1,2-dithiolato-S,µS′)technetium(V)oxo(ethan- 1,2-dithiolato-S,S′)technetium(V) [(TcO)2(SCH2CH2S)3]. A Tc(V) compound containing metal—sulfur—metal bridges

“…The remaining sulfur atoms, S(4) and S(6), are also bonded to Tc(2). This type of bridging sulfur has been observed previously for the (NH2CH2CH2S)-ligand in the [Ni,(SCH2CH2NH2)4]'t cation (24). The structure of I thus has four distinct types of Tc-S bonds.…”

The crystal and molecular structure of bis(thioglycinato)nickel(II)

“…There, the Ni-N distance is 0.04 A longer than that found in this work, presumably due to the effect of the amino methyl groups (Girling & Amma, 1967). Altogether, the Ni-S, C-N, and C-C bond lengths found lie in the range of those given in a recent tabulation (Wei & Dahl, 1970) of bond lengths found in square-planar Ni(II) complexes of 2-amino-ethanethiol and its derivatives. The Ni-N distance is 0.02 A longer in bis(thioglycinato)nickel(II) than that given in the above tabulation, but the S-C distance is 0.11 A shorter, indicating that the S-C bond has appreciable multiple-bond character.…”

“…The diamagnetism of this complex and its electronic spectrum show that Ni(II) lies in a square-planar environment, but the low solubility of bis(thioglycinato)nickel(II) does not allow dipole moment measurements to be made to determine whether the coordinating ligands are arranged acentrically, as had been found in the structure of tetrakis-(2-aminoethanethiol)-trinickel(II) chloride (Wei & Dahl, 1970), or centrically as found in bis-(N,N-dimethyl-2-aminoethanethiol)-nickel(II) (Girling & Aroma, 1967). In bis(glycinato)-nickel(II) dihydrate (Okaya, Pepinsky, Takeuchi, Kuroya, Shimada, Gallitelli, Stemple & Beevers, 1957) (Freeman & Guss, 1968), centric coordination is found.…”

New nickel complexes with an S4 coordination sphere; synthesis, characterization and reactivity towards nickel and iron compounds

“…The angle formed between the planes, Ni(1)S 2 S 0 2 -Ni(2)S 4 is 68.24(19)°. Several compounds have been reported to have a similar structure [10,[25][26][27][28][29][30].…”