Abstract
[Ni(4-mpipdtc)2] and [Ni(4-mpipdtc)(PPh3)(NCS)] (4-mpipdtc = 4-methylpiperidinecarbodithioate anion) have been characterized by electronic, IR, and NMR spectroscopy, single crystal X-ray analysis, and cyclic voltammetry. IR spectra of the complexes show the contribution of the thioureide form to the structures. 1H NMR spectra show the deshielding of α-CH2 protons on complexation. 13C NMR spectra shows interesting differences between the N13CS2 carbon signals of the parent complex [Ni(4-mpipdtc)2] and the mixed ligand complex [Ni(4-mpipdtc)(PPh3)(NCS)]. The N13CS2 carbon signal for [Ni(4-mpipdtc)(PPh3)(NCS)] is observed at 204.85 ppm with an upfield shift of about 3.8 ppm compared with that found in [Ni(4-mpipdtc)2] (201.06 ppm). The observed shielding in [Ni(4-mpipdtc)(PPh3)(NCS)] indicates the effect of PPh3 on the mesomeric drift of electron density toward nickel through the thioureide C–N bond. Single crystal X-ray analysis of [Ni(4-mpipdtc)2] and [Ni(4-mpipdtc)(PPh3)(NCS)] confirms the presence of four-coordinated nickel in a distorted square-planar arrangement with the NiS4 and NiS2PN chromophores, respectively. The C–N (thioureide) bond lengths of [Ni(4-mpipdtc)(PPh3)(NCS)] are shorter than those found in [Ni(4-mpipdtc)2], because of the presence of the π-acid (triphenylphosphine) in [Ni(4-mpipdtc)(PPh3)(NCS)]. Significant asymmetry in Ni–S bond distances was observed in Ni(4-mpipdtc)(PPh3)(NCS)] (2.162(2) and 2.211(2) Å). This observation clearly supports the less effective trans effect of SCN– over PPh3. The piperidine ring in the dithiocarbamate fragment is in the normal chair conformation.
Graphical Abstract
Similar content being viewed by others
References
Cox MJ, Tiekink ERT (1997) Rev Inorg Chem 17:1
Heard J (2005) Prog Inorg Chem 53:1
Nan Y, Yang Z (1999) Tetrahedron Lett 40:2323
Srogl J, Liu W, Marshall D, Liebeskind LS (1999) J Am Chem Soc 121:9449
Sambaiah T, Li L, Huang D, Lin C, Rayabarapu DK, Cheng C (1999) J Org Chem 64:3663
Jarrett PS, Dhubhghaill OMN, Sadler PJ (1993) J Chem Soc Dalton Trans 1863
Bonamico M, Destry G, Mariani C, Vaciago A, Zambonelli L (1965) Acta Crystallogr B 19:619
Uppadine LH, Weeks JM, Beer PD (2001) J Chem Soc Dalton Trans 3367
Chakrawarty A (1966) Prog Inorg Chem 7:83
Fackler JP Jr, Seigel WC (1969) Inorg Chem 8:1631
Jorgensen CK (1964) Inorg Chem 3:1201
Ramalingam K, Aravamudan G, Venkatachalam V (1993) Bull Chem Soc Japan 66:1554
Arul Prakasam B, Ramalingam K, Saravanan M, Bocelli G, Contoni A (2004) Polyhedron 23:77
Bonati F, Ugo R (1967) J Organomet Chem 110:257
Cernickova JE, Chartonik IA, Umrejko DS, Kavirikov VI (1989) Coord Chem 15:1695
Lever ABP (1968) Inorganic electronic spectroscopy. Elsevier, Amsterdam, p 343
Tsipis CA, Meleziadis IJ, Kessissoglou DP, Kotsolos GA (1984) Inorg Chim Acta 90:L19
Arulprakasam B, Ramalingam K, Bocelli G, Cantoni A (2007) Polyhedron 26:4489
Ivanov AV, Roduia T, Antzutkin ON (1998) Polyhedron 17:3101
Higgins GMC, Saville B (1963) J Chem Soc 2812
Ramalingam K, Radha K, Aravamudan G, Mahadevan C, Subramaniyam CH, Seshasayee M (1984) Acta Crystallogr C 40:1838
Ramalingam K, Aravamudan G, Seshasayee M (1987) Inorg Chim Acta 128:231
Ahomre A, Burla ML, Camalli M, Cascavano G, Giacovazzo G, Gugaliardi A, Polidori G (1994) J Appl Crystallogr 27:4385
Sheldrick GM (1997) SHELXL 97. University of Göttingen, Göttingen
Fabretti AC, Franchini GC, Pretic C, Toshi G, Zannini P (1985) Transit Met Chem 10:284
Acknowledgments
We are thankful to SAIF, Indian Institute of Technology, Madras for the single crystal X-ray structural analysis.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Srinivasan, N., Sathyaselvabala, V., Kuppulekshmy, K. et al. Structural variations of nickel complexes in NiS4 and NiS2PN coordination environments: spectral and single-crystal X-ray structural studies on bis(4-methylpiperidinecarbodithioato-S,S′)nickel(II) and (4-methylpiperidinecarbodithioato-S,S′)(thiocyanato-N)(triphenylphosphine)nickel(II). Monatsh Chem 140, 1431–1436 (2009). https://doi.org/10.1007/s00706-009-0199-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00706-009-0199-2