Syntheses, X-ray Crystal Structures, and Spectroscopic Properties of New Nickel Dithiolenes and Related Compounds
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- 作者：Francesco Bigoli ; Paola Deplano ; Francesco A. Devillanova ; John. R. Ferraro ; Vito Lippolis ; Peter J. Lukes ; Maria Laura Mercuri ; Maria Angela Pellinghelli ; Emanuele F. Trogu ; and Jack M. Williams
- 刊名：Inorganic Chemistry
- 出版年：1997
- 出版时间：March 12, 1997
- 年：1997
- 卷：36
- 期：6
- 页码：1218 - 1226
- 全文大小：519K
- 年卷期：v.36,no.6(March 12, 1997)
- ISSN：1520-510X
文摘
The direct addition of nickel powder to the reaction mixtures of1,3-dialkyl-4,5-dioxoimidazolidine-2-thione (1)with the thionation Lawesson reagent produces[NiII(R2timdt-)2](R2timdt =1,3-dialkylmidazolidine-2,4,5-trithione).These complexes belong to a new class of nickel-dithiolenes,showing remarkably high absorption (
chars/epsilon.gif" BORDER=0 > 
80 000dm3 mol-1cm-1, chars/lambda.gif" BORDER=0 > 1000 nm) in the near-infraredregion (near-IR), accompanied by high photochemicalstabilitythat makes these complexes promising near-IR dyes. In the absenceof nickel the reaction yields generally thecompounds4,5,6,7-tetrathiocino[1,2-b:3,4-b']diimidazolyl-1,3,8,10-tetraalkane-2,9-dithione(2) instead of theexpected 1,3-dialkylimidazolidine-2,4,5-trithione. However, withbulky substituents on the nitrogen atoms, well-characterized reaction products have not been obtained until now.Only in the R = Pri case, the newtetrathiocinoisomer(4,5,9,10-tetrathiocino[1,2-b:5,6-b']diimidazolyl-1,3,6,8-tetraisopropane-2,7-dithione(3) in trace amountsand the bis(1,3-diisopropyl-2-thioxoimidazolin-4-yl) disulfide(4) were isolated from the reaction with theLawessonreagent and P4S10, respectively. Reactionof 5 with different amounts of I2 leads to avariety of products, andamong them the following derivatives have been characterized:[NiII(Pri2timdt-)2]·2I2(6) a neutral adduct inwhich each I2 molecule interacts with each peripheralthione sulfur atom of 5;[NiII(Pri2timdt-)2]·2I2·1/2I2(7),which differs from 6 with the presence of half diiodine as aguest; with a larger diiodine excess (starting from a1:10 molar ratio) a partial oxidation of 5 is achieved and[NiII(Pri2timdt-)2][NiII(I)2(Pri2timdt)2]·5I2(8) is formed,a ligand mixed-valence compound in which the square-planar complex5 and the octahedral complex[NiII(I)2(Pri2timdt)2] (the ligand in neutral form) are bound by diiodinemolecules in such a way that a sequence of 12 iodineatoms(S·I2···I2···I-···I2···I-···I2···I2·S)is formed. Spectroscopic and X-ray diffractometric studies of3(monoclinic, space group P21/n,a = 13.104(6) Å, b = 15.091(6) Å,c = 6.067(7) Å, chars/beta2.gif" BORDER=0 ALIGN="middle"> = 103.00(2)
,Z = 2), 4(monoclinic, space group C2/c, a =18.717(5) Å, b = 8.846(5) Å, c =14.475(5) Å, chars/beta2.gif" BORDER=0 ALIGN="middle"> = 97.78(2), Z = 4),5(orthorhombic, space group Pna21, a= 18.806(5) Å, b = 5.628(7) Å, c= 23.665(5) Å, Z = 4), 7 (triclinic,spacegroup P
cr.gif">, a = 9.126(7) Å,b = 9.153(7) Å, c = 12.924(6) Å,chars/alpha.gif" BORDER=0> = 82.11(2), chars/beta2.gif" BORDER=0 ALIGN="middle"> = 70.14(2), chars/gamma.gif" BORDER=0 > = 72.51(2),Z =1), and 8 (monoclinic, space groupC2/c, a = 21.971(6) Å,b = 28.081(5) Å, c = 12.207(8) Å,chars/beta2.gif" BORDER=0 ALIGN="middle"> = 93.57(2),Z = 4) are given.
chars/epsilon.gif" BORDER=0 > 80 000dm3 mol-1cm-1, chars/lambda.gif" BORDER=0 > 1000 nm) in the near-infraredregion (near-IR), accompanied by high photochemicalstabilitythat makes these complexes promising near-IR dyes. In the absenceof nickel the reaction yields generally thecompounds4,5,6,7-tetrathiocino[1,2-b:3,4-b']diimidazolyl-1,3,8,10-tetraalkane-2,9-dithione(2) instead of theexpected 1,3-dialkylimidazolidine-2,4,5-trithione. However, withbulky substituents on the nitrogen atoms, well-characterized reaction products have not been obtained until now.Only in the R = Pri case, the newtetrathiocinoisomer(4,5,9,10-tetrathiocino[1,2-b:5,6-b']diimidazolyl-1,3,6,8-tetraisopropane-2,7-dithione(3) in trace amountsand the bis(1,3-diisopropyl-2-thioxoimidazolin-4-yl) disulfide(4) were isolated from the reaction with theLawessonreagent and P4S10, respectively. Reactionof 5 with different amounts of I2 leads to avariety of products, andamong them the following derivatives have been characterized:[NiII(Pri2timdt-)2]·2I2(6) a neutral adduct inwhich each I2 molecule interacts with each peripheralthione sulfur atom of 5;[NiII(Pri2timdt-)2]·2I2·1/2I2(7),which differs from 6 with the presence of half diiodine as aguest; with a larger diiodine excess (starting from a1:10 molar ratio) a partial oxidation of 5 is achieved and[NiII(Pri2timdt-)2][NiII(I)2(Pri2timdt)2]·5I2(8) is formed,a ligand mixed-valence compound in which the square-planar complex5 and the octahedral complex[NiII(I)2(Pri2timdt)2] (the ligand in neutral form) are bound by diiodinemolecules in such a way that a sequence of 12 iodineatoms(S·I2···I2···I-···I2···I-···I2···I2·S)is formed. Spectroscopic and X-ray diffractometric studies of3(monoclinic, space group P21/n,a = 13.104(6) Å, b = 15.091(6) Å,c = 6.067(7) Å, chars/beta2.gif" BORDER=0 ALIGN="middle"> = 103.00(2),Z = 2), 4(monoclinic, space group C2/c, a =18.717(5) Å, b = 8.846(5) Å, c =14.475(5) Å, chars/beta2.gif" BORDER=0 ALIGN="middle"> = 97.78(2), Z = 4),5(orthorhombic, space group Pna21, a= 18.806(5) Å, b = 5.628(7) Å, c= 23.665(5) Å, Z = 4), 7 (triclinic,spacegroup Pcr.gif">, a = 9.126(7) Å,b = 9.153(7) Å, c = 12.924(6) Å,chars/alpha.gif" BORDER=0> = 82.11(2), chars/beta2.gif" BORDER=0 ALIGN="middle"> = 70.14(2), chars/gamma.gif" BORDER=0 > = 72.51(2),Z =1), and 8 (monoclinic, space groupC2/c, a = 21.971(6) Å,b = 28.081(5) Å, c = 12.207(8) Å,chars/beta2.gif" BORDER=0 ALIGN="middle"> = 93.57(2),Z = 4) are given.