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2012 | 10 | 4 | 1199-1207
Tytuł artykułu

Trans influence of triphenylphosphines and pseudohalogens on Ni-S bonds: Synthesis, spectral and single crystal X-ray structural studies on NiS2PN and NiS2PC chromophores

Treść / Zawartość
Warianty tytułu
Języki publikacji
EN
Abstrakty
EN
Trans influence of triphenylphosphines and pseudohalogens on Ni-S bonds of NiS2PN and NiS2PC chromophores has been investigated by synthesizing and characterizing them. The complexes show the characteristic thioureide IR band at ∼ 1530 cm−1. Electronic spectrum of the cyanide analogue shows a strong blue shift relative to others. X-ray structures of [Ni(pipdtc)(4-MP)(NCS)] (1), [Ni(pipdtc)(PPh3)(NCS)] (2) and [Ni(pipdtc)(PPh3)(CN)] (3) (pipdtc = piperidinecarbodithioate anion, 4-MP = tri(4-methylphenyl)phopshine) are reported. Ni-S bond distance trans to 4-MP(1) is longer than the distances in (2) and (3) and Ni-S bond distances trans to Ni-NCS/CN decrease as follows: (3) > (2) > (1). Particularly, 4-MP shows a highly significant trans influence than triphenylphosphine on Ni-S bond. Similarly, CN− exerts a marginally significant trans influence compared to NCS-. Thioureide C-N distances are relatively very short due to the drift of electron density towards the metal. The Ni-N-C angle (163.5(2)°) observed in (2) indicates deviation from linearity to a larger extent compared to that in (1) (176.3(3)°) due to the steric effect of the 4-methyl group. The reduction potentials (CV) for the mixed ligand complexes are much less compared to that of the parent NiS4 chromophore due to the π-acidic phosphines. [...]
Wydawca

Czasopismo
Rocznik
Tom
10
Numer
4
Strony
1199-1207
Opis fizyczny
Daty
wydano
2012-08-01
online
2012-05-29
Twórcy
  • Department of Chemistry, Annamalai University, Annamalainagar, 608 002, India, krauchem@yahoo.com
  • Department of Chemistry, Anna University of Technology, Tiruchirappalli, 620 024, India
  • IMEM-CNR, Parco Area Delle Scienze, Parma, 43100, Italy
autor
  • IMEM-CNR, Parco Area Delle Scienze, Parma, 43100, Italy
Bibliografia
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Typ dokumentu
Bibliografia
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Identyfikator YADDA
bwmeta1.element.-psjd-doi-10_2478_s11532-012-0041-2
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