“…Ni−C distances and ν(CN) bands for 2 with those of 3 and 4 below). In the equatorial plane, the Ni atom and the two dithiolato ligands are arranged in a fashion very close to that found in the structural determination of the square-planar starting compound 1 . 1 Perspective view of one of the two crystallographically independent but chemically equivalent molecules of [Ni{S 2 P(OEt) 2 } 2 (CNXyl) 2 ] ( 2 ), showing the atom numbering.…”
[Ni{S2P(OEt)2}2] (1) reacts with 2 equiv of CNXyl (Xyl = 2,6-dimethylphenyl) to afford
[Ni{S2P(OEt)2}2(CNXyl)2] (2), which, as confirmed by X-ray crystallography, is the first
octahedral isocyanide complex of Ni(II). Reaction of 2 with PCy3 (2 equiv) produces square-planar [Ni{S2P(O)(OEt)}(PCy3)(CNXyl)] (3). When 2 is reacted with only 1 equiv of PCy3,
the final product is the square-planar complex [Ni{S2P(O)(OEt)}(CNXyl)2] (4), containing
two isocyanide ligands. Compound 4 reacts with 2-fold excess PCy3 to give 3 via isocyanide
displacement. Both 3 and 4 contain one ethyldithiophosphate ligand, which is produced by
the transfer of one ethyl group from a coordinated diethyl dithiophosphate of complex 2 to
the leaving diethyl dithiophosphate ligand. Experimental evidence indicates that the
phosphine plays a significant role in the alkyl transfer. Moreover, reaction of 1 with 2 equiv
of N
-
p-tolyl-2-iminopyridine affords octahedral [Ni{S2P(OEt)2}{2-pyCHNC6H4-Me-4}2][S2P(OEt)2] (5), in which both free and coordinated diethyl dithiophosphate coexist without any
transfer of alkyl.
“…Ni−C distances and ν(CN) bands for 2 with those of 3 and 4 below). In the equatorial plane, the Ni atom and the two dithiolato ligands are arranged in a fashion very close to that found in the structural determination of the square-planar starting compound 1 . 1 Perspective view of one of the two crystallographically independent but chemically equivalent molecules of [Ni{S 2 P(OEt) 2 } 2 (CNXyl) 2 ] ( 2 ), showing the atom numbering.…”
[Ni{S2P(OEt)2}2] (1) reacts with 2 equiv of CNXyl (Xyl = 2,6-dimethylphenyl) to afford
[Ni{S2P(OEt)2}2(CNXyl)2] (2), which, as confirmed by X-ray crystallography, is the first
octahedral isocyanide complex of Ni(II). Reaction of 2 with PCy3 (2 equiv) produces square-planar [Ni{S2P(O)(OEt)}(PCy3)(CNXyl)] (3). When 2 is reacted with only 1 equiv of PCy3,
the final product is the square-planar complex [Ni{S2P(O)(OEt)}(CNXyl)2] (4), containing
two isocyanide ligands. Compound 4 reacts with 2-fold excess PCy3 to give 3 via isocyanide
displacement. Both 3 and 4 contain one ethyldithiophosphate ligand, which is produced by
the transfer of one ethyl group from a coordinated diethyl dithiophosphate of complex 2 to
the leaving diethyl dithiophosphate ligand. Experimental evidence indicates that the
phosphine plays a significant role in the alkyl transfer. Moreover, reaction of 1 with 2 equiv
of N
-
p-tolyl-2-iminopyridine affords octahedral [Ni{S2P(OEt)2}{2-pyCHNC6H4-Me-4}2][S2P(OEt)2] (5), in which both free and coordinated diethyl dithiophosphate coexist without any
transfer of alkyl.
“…To the extent that bond lengths reflect bond energies, A77Mt-p(M-L) will be positive since the high-spin form of a given metal ion generally has a larger ionic radius than the low-spin form. This is the situation found in a comparison of tetrahedral bis (N-isopropylsalicylaldimino) -31 and bis(3-ethyl-Nisopropylsalicylaldimino) nickel (I I)8 9 with planar bis-(3-methyl-N-isopropylsalicylaldimino)nickel(II)30 for which the Ni-0 and Ni-N distances are 0.05-0.06 A longer in the tetrahedral complex. AHc0-n/ -p (M-L) is expected to be nonzero when the R groups are the same and will presumably be somewhat larger when they are different.…”
“…The nickel atom of Ni(DEDTP) 2 molecule ( Fig. 1) occupies a crystallographic inversion centre and shows a square planar geometry, which was also observed previously by Fernando & Green (Fernando & Green, 1967;NIETHP01) and McConnell & Kastalsky (McConnell & Kastalsky, 1967;NIETHP), who used multiple film technique data for the structure determination. For NIETHP01 (R = 15.7%) the average distances and angles within four-membered NiS 2 P chelate ring were given as Ni-S 2.21 (1) Å, P-S 1.97 (2) Å, S1-Ni-S2 88°, and S1-P-S2 103°.…”
Section: S1 Commentsupporting
confidence: 74%
“…For the syntheses and structure of a series of homologous Ni(S 2 P{OR} 2 ) 2 complexes, see: R = Me: Kastalsky & McConnell (1969); R = Et: Fernando & Green (1967); McConnell & Kastalsky (1967); R = Pr and R = i Bu: Ivanov et al (2004); R = i Pr: Tkachev & Atovmyan (1976); Hoskins & Tiekink (1985). For complexes with sulfur-rich kernel-bearing silanethiolato and dithiocarbamato ligands, see: Kropidłowska et al (2008).…”
The centrosymmetric title complex, [Ni{S2P(OC2H5)2}2], has been redetermined using area-detector data. The central Ni(S2P)2 core is essentially planar and confirms the early results of McConnell & Kastalsky [Acta Cryst. (1967), 22, 853–859] based on multiple film technique data. In the title structure, the standard uncertainty values are approximately seven times lower and all H-atom positions are calculated. A pair of short symmetry-related H⋯H contacts with distances of 2.33 Å is observed in the crystal structure.
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