Synthesis and spectroscopic investigation of some mixed-ligand nickel(II) chelates containing phosphines and 1,1-dithiolate ligands. Crystal structure of [(1,2-bis(diphenylphosphino)ethane)-1,1-dicyano-2,2-ethylenedithiolato]nickel(II)

Hadjikostas, C. C.; Alkam, Hussein; Bolos, C.A.; Christidis, P. C.

doi:10.1016/s0277-5387(00)00642-2

Cited by 10 publications

(9 citation statements)

References 31 publications

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“…These shifts reveal an increase of the order of the C"N and C@C bonds, since the planar extensive p-conjugated system of the i-MNT ligand facilitate a drift of electron density towards the sulfur atoms that results in a shortening of the C"N and C@C bonds. 20 The medium intensity bands at 943-989 cm À1 and 794-896 cm À1 in the IR spectra are assigned to m as (CS 2 ) and m sym (CS 2 ), respectively.…”

Section: Ir Spectral Studiesmentioning

confidence: 99%

“…The small S-Ni-S chelation angle of 78.85(2)°indi-cates that it is determined by the geometry of the rigid i-MNT ligand. 19,20 On the other hand, as a result of the relatively small separation of the coordinated nitrogen atoms of the flexible 2a-5mt ligands (2.851 Å in comparison to 3.10 Å, which is the sum of their van der Waals radii) the opposite N-Ni-N angle appears greater than the ideal value of 90°[95.26(7)°]. The two Ni-S distances are very close to each other and have a mean value of 2.189(1) Å, which is in very good agreement with the corresponding ones observed in other dithiolato complexes, having the Ni(II) atom in a square-planar coordination.…”

Section: Description Of the Structure Of [Ni(i-mnt)(2a-5mt) 2 ]mentioning

confidence: 99%

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Characterization and DNA-interaction studies of 1,1-dicyano-2,2-ethylene dithiolate Ni(II) mixed-ligand complexes with 2-amino-5-methyl thiazole, 2-amino-2-thiazoline and imidazole. Crystal structure of [Ni(i-MNT)(2a-5mt)2]

Cox¹,

Psomas²,

Bolos³

2009

Bioorganic & Medicinal Chemistry

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Section: Ir Spectral Studiesmentioning

confidence: 99%

Section: Description Of the Structure Of [Ni(i-mnt)(2a-5mt) 2 ]mentioning

confidence: 99%

Characterization and DNA-interaction studies of 1,1-dicyano-2,2-ethylene dithiolate Ni(II) mixed-ligand complexes with 2-amino-5-methyl thiazole, 2-amino-2-thiazoline and imidazole. Crystal structure of [Ni(i-MNT)(2a-5mt)2]

Cox¹,

Psomas²,

Bolos³

2009

Bioorganic & Medicinal Chemistry

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“…11 The 1,1-ethylenedithiolato ligands have also been used to stabilize unusually high oxidation states [12][13][14] or to facilitate the syntheses of clusters. [15][16][17][18][19][20][21] Most 1,1-ethylenedithiolato complexes are mononuclear 7-9,12-14, [22][23][24][25][26][27] although some polynuclear complexes [28][29][30][31] including clusters 15,18,19,[32][33][34][35][36][37] are known.…”

Section: Introductionmentioning

confidence: 99%

“…13 C-DEPT{1H} NMR: δ 21 26. [s, Me (Xy)], 35.34 [s, C(O)Me], 131.28 (s, p-CH, Xy), 131.83 (s, m-CH, Xy).…”

mentioning

confidence: 99%

1,1-Ethylenedithiolato Complexes of Palladium(II) and Platinum(II) with Isocyanide and Carbene Ligands

et al. 2003

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The reactions of [Tl(2)[S(2)C=C[C(O)Me](2)]](n) with [MCl(2)(NCPh)(2)] and CNR (1:1:2) give complexes [M[eta(2)-S(2)C=C[C(O)Me](2)](CNR)(2)] [R = (t)Bu, M = Pd (1a), Pt (1b); R = C(6)H(3)Me(2)-2,6 (Xy), M = Pd (2a), Pt (2b)]. Compound 1b reacts with AgClO(4) (1:1) to give [[Pt(CN(t)Bu)(2)](2)Ag(2)[mu(2),eta(2)-(S,S')-[S(2)C=C[C(O)Me](2)](2)]](ClO(4))(2) (3). The reactions of 1 or 2 with diethylamine give mixed isocyanide carbene complexes [M[eta(2)-S(2)C=C[C(O)Me](2)](CNR)[C(NEt(2))(NHR)]] [R = (t)Bu, M = Pd (4a), Pt (4b); R = Xy, M = Pd (5a), Pt (5b)] regardless of the molar ratio of the reagents. The same complexes react with an excess of ammonia to give [M[eta(2)-(S,S')-S(2)C=C[C(O)Me](2)](CN(t)Bu)[C(NH(2))(NH(t)Bu)]] [M = Pd (6a), Pt (6b)] or [M[eta(2)-(S,S')-S(2)C=C[C(O)Me](2)][C(NH(2))(NHXy)](2)] [M = Pd (7a), Pt (7b)] probably depending on steric factors. The crystal structures of 2b, 4a, and 4b have been determined. Compounds 4a and 4b are isostructural. They all display distorted square planar metal environments and chelating planar E,Z-2,2-diacetyl-1,1-ethylenedithiolato ligands that coordinate through the sulfur atoms.

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“…As compared to the complexes with the mnt 2- ligand, those with the i-mnt 2- ligand have received less attention, , although i-mnt 2- has the two important features. First, i-mnt 2- may possess greater electron delocalization through the S−C, CC, and C−CN bonds, which was suggested by studies of surface-enhanced Raman scattering .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactions of Group 6 Metal Half-Sandwich Complexes of 2,2-Dicyanoethylene-1,1-dichalcogenolates [(Cp*)M{E₂CC(CN)₂}₂]^- (M = Mo, W; E = S, Se)

et al. 2002

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A series of group 6 transition metal half-sandwich complexes with 1,1-dichalcogenide ligands have been prepared by the reactions of Cp*MCl(4)(Cp* = eta(5)-C(5)Me(5); M = Mo, W) with the potassium salt of 2,2-dicyanoethylene-1,1-dithiolate, (KS)(2)C=C(CN)(2) (K(2)-i-mnt), or the analogous seleno compound, (KSe)(2)C=C(CN)(2) (K(2)-i-mns). The reaction of Cp*MCl(4) with (KS)(2)C=C(CN)(2) in a 1:3 molar ratio in CH(3)CN gave rise to K[Cp*M(S(2)C=C(CN)(2))(2)] (M = Mo, 1a, 74%; M = W, 2a, 46%). Under the same conditions, the reaction of Cp*MoCl(4) with 3 equiv of (KSe)(2)C=C(CN)(2) afforded K[Cp*Mo(Se(2)C=C(CN)(2))(2)] (3a) and K[Cp*Mo(Se(2)C=C(CN)(2))(Se(Se(2))C=C(CN)(2))] (4) in respective yields of 45% and 25%. Cation exchange reactions of 1a, 2a, and 3a with Et(4)NBr resulted in isolation of (Et(4)N)[Cp*Mo(S(2)C=C(CN)(2))(2)] (1b), (Et(4)N)[Cp*W(S(2)C=C(CN)(2))(2)] (2b), and (Et(4)N)[Cp*Mo(Se(2)C=C(CN)(2))(2)] (3b), respectively. Complex 4 crystallized with one THF and one CH(3)CN molecule as a three-dimensional network structure. Inspection of the reaction of Cp*WCl(4) with (KSe)(2)C=C(CN)(2) by ESI-MS revealed the existence of three species in CH(3)CN, [Cp*W(Se(2)C=C(CN)(2))(2)]-, [Cp*W(Se(2)C=C(CN)(2))(Se(Se(2))C=C(CN)(2))]-, and [Cp*W(Se(Se(2))C=C(CN)(2))(2)]-, of which [Cp*W(Se(2)C=C(CN)(2))(Se(Se(2))C=C(CN)(2))]-(5) was isolated as the main product. Treatment of 2a with 1/4 equiv of S(8) in refluxing THF resulted in sulfur insertion and gave rise to K[Cp*W(S(2)C=C(CN)(2))(S(S(2))C=C(CN)(2))](6), which crystallized with two THF molecules forming a three-dimensional network structure. 6 can also be prepared by refluxing 2a with 1/4 equiv of S(8) in THF. 3a readily added one Se atom upon treatment with 1 mol of Se powder in THF to give 4 in high yield, while the treatment of 3a or 4 with 2 equiv of Na(2)Se in THF led to formation of a dinuclear complex [(Cp*Mo)(2)(mu-Se)(mu-Se(Se(3))C=C(CN)(2))] (7). The structure of 7 consists of two Cp*Mo units bridged by a Se(2-) and a [Se(Se(3))C=C(CN)(2)](2-) ligand in which the triselenido group is arranged in a nearly linear way (163 degrees). The reaction of 2a with 2 equiv of CuBr in CH(3)CN yielded a trinuclear complex [Cp*WCu(2)(mu-Br)(mu(3)-S(2)C=C(CN)(2))(2)] (8), which crystallized with one CH(3)CN and generated a one-dimensional chain polymer through bonding of Cu to the N of the cyano groups.

show abstract

Synthesis and spectroscopic investigation of some mixed-ligand nickel(II) chelates containing phosphines and 1,1-dithiolate ligands. Crystal structure of [(1,2-bis(diphenylphosphino)ethane)-1,1-dicyano-2,2-ethylenedithiolato]nickel(II)

Cited by 10 publications

References 31 publications

Characterization and DNA-interaction studies of 1,1-dicyano-2,2-ethylene dithiolate Ni(II) mixed-ligand complexes with 2-amino-5-methyl thiazole, 2-amino-2-thiazoline and imidazole. Crystal structure of [Ni(i-MNT)(2a-5mt)2]

Characterization and DNA-interaction studies of 1,1-dicyano-2,2-ethylene dithiolate Ni(II) mixed-ligand complexes with 2-amino-5-methyl thiazole, 2-amino-2-thiazoline and imidazole. Crystal structure of [Ni(i-MNT)(2a-5mt)2]

1,1-Ethylenedithiolato Complexes of Palladium(II) and Platinum(II) with Isocyanide and Carbene Ligands

Synthesis and Reactions of Group 6 Metal Half-Sandwich Complexes of 2,2-Dicyanoethylene-1,1-dichalcogenolates [(Cp*)M{E₂CC(CN)₂}₂]^- (M = Mo, W; E = S, Se)

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Synthesis and spectroscopic investigation of some mixed-ligand nickel(II) chelates containing phosphines and 1,1-dithiolate ligands. Crystal structure of [(1,2-bis(diphenylphosphino)ethane)-1,1-dicyano-2,2-ethylenedithiolato]nickel(II)

Cited by 10 publications

References 31 publications

Characterization and DNA-interaction studies of 1,1-dicyano-2,2-ethylene dithiolate Ni(II) mixed-ligand complexes with 2-amino-5-methyl thiazole, 2-amino-2-thiazoline and imidazole. Crystal structure of [Ni(i-MNT)(2a-5mt)2]

Characterization and DNA-interaction studies of 1,1-dicyano-2,2-ethylene dithiolate Ni(II) mixed-ligand complexes with 2-amino-5-methyl thiazole, 2-amino-2-thiazoline and imidazole. Crystal structure of [Ni(i-MNT)(2a-5mt)2]

1,1-Ethylenedithiolato Complexes of Palladium(II) and Platinum(II) with Isocyanide and Carbene Ligands

Synthesis and Reactions of Group 6 Metal Half-Sandwich Complexes of 2,2-Dicyanoethylene-1,1-dichalcogenolates [(Cp*)M{E2CC(CN)2}2]- (M = Mo, W; E = S, Se)

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Synthesis and Reactions of Group 6 Metal Half-Sandwich Complexes of 2,2-Dicyanoethylene-1,1-dichalcogenolates [(Cp*)M{E₂CC(CN)₂}₂]^- (M = Mo, W; E = S, Se)