Conformations and coordination properties of trialkyltrithiophosphites in copper(I) complexes

Kataeva, О. N.; Krivolapov, Dmitry B.; Gubaidullin, А. Т.; Литвинов, И. А.; Kursheva, L. I.; Katsyuba, Sergey A.

doi:10.1016/s0022-2860(00)00665-7

Cited by 16 publications

(12 citation statements)

References 14 publications

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“…The P-S bond length is 2.126 Å and the P-S-C angle 99.6°. Upon coordination to AuCl, the P-S bonds undergo a significant shortening to 2.094 (2) In contrast to 1, polymorphs A and B (both in space group P 1, Z = 4 for A and Z = 2 for B) of 2 (Figs. 5 and 6) do not exhibit aurophilic interactions, which may be due to the prevalence of other association phenomena discussed below as steric factors are not likely to contribute.…”

Section: Crystallographymentioning

confidence: 99%

“…This may be in part owing to the properties of trithiophosphites whose odour and toxicity render them unattractive substrates of study. A recent paper by Kataeva et al summarises trithiophosphite coordination chemistry [2]. A limited number of crystal structures have been published for a series of trithiophosphite (L) complexes of copper(I) halides and pseudohalides [2,3], two CpMn(CO) 2 L-type compounds [4], an (arene)Cr(CO) 2 L [5] and one each of di-and trinuclear iron carbonyl complexes [6].…”

Section: Introductionmentioning

confidence: 99%

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The preparation, properties and X-ray structures of gold(I) trithiophosphite complexes

Strasser

Cronje

Schmidbaur

et al. 2006

Journal of Organometallic Chemistry

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Section: Crystallographymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

The preparation, properties and X-ray structures of gold(I) trithiophosphite complexes

Strasser

Cronje

Schmidbaur

et al. 2006

Journal of Organometallic Chemistry

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“…The precipitate of IIc was filtered off; yield 1.05 g (80%), mp 1483150oC. The product is insoluble in CH 3 CN, C 6 H 6 , CHCl 3 , CH 2 Cl 2 , C 6 …”

Section: Methodsmentioning

confidence: 99%

“…We showed previously that trithiophosphites in transition metal complexes are characterized by a wide diversity of conformations, untypical of the [free] molecules [6,7]. If a unit cell contained several independent molecules, the conformational nonuniformity was often observed.…”

mentioning

confidence: 99%

Synthesis and Structure of Copper(II) Phosphonodithioite Complexes

et al. 2005

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A series of new complexes of CuBr with phosphonodithioites were prepared and characterized by NMR and IR spectroscopy. As shown by single crystal X-ray diffraction, diethyl tert-butylphosphonodithioite forms with CuBr a tetrameric cubane-like complex with the monodentate coordination of the organophosphorus ligand via the P atom.Our previous studies [137] showed that complexes formed by phosphorothoite with transition metals are more diverse in the structure and coordination mode than complexes formed by other trivalent phosphorus compounds, in particular, phosphines, phosphites, and amides [8313]. This is due to the specific electronic structure of the ligand molecules containing P3S ambident systems [14]. It can be expected that the replacement of one of the SR groups in a phosphorothoite molecule by an alkyl group will alter the donor properties of the P and S atoms and hence the coordination properties of the ligand. A search in the Cambridge Structural Database [15] revealed no data on the crystal structure of phosphorothoite complexes. Copper(I) phosphorothoite complexes, in which the ligand molecule contains a P3C bond along with two P3S bonds, are of interest from the viewpoint of ligand reactivity in the metal coordination sphere. Our previous studies of copper thiophosphite complexes revealed such phenomena as ligand exchange, disproportionation, ligand transformation, and formation of ligands of a new structure in the metal coordination sphere [2,5,16,17].Here we report on the complexation of CuBr with a series of diethyl phosphonodithioites containing ethyl, phenyl, and tert-butyl substituents at the P atom. Thiophosphonites Ia3Ic readily react with CuBr. Complexes IIb and IIc are colorless crystalline substances. According to elemental analysis, the reaction products have 1 : 1 composition. Complexes IIb and IIc are formed in fairly high yields (80 385%).Compound IIb is soluble in the majority of organic solvents. Complex IIc is insoluble in organic solvents, RP(SEt) 2 + CuBr 76 RP(SEt) 2 .CuBr,including DMSO and DMF. Complex IIa was isolated as an oily precipitate; it rapidly darkens, which suggests its instability and possible decomposition. Products of its secondary transformations were not studied.Complexes IIa3IIc were studied by IR spectroscopy (solid samples). According to the IR data, the P3C stretching frequency does not noticeably change upon complexation and remains about 750 cm !1 . At the same time, the P3S bands in the spectra of the complexes become more intense compared to the free ligands and are shifted toward higher frequencies bỹ 20 cm !1 . To compare, in the case of bidentate coordination of triethyl phosphorotrithioite, the shift is toward lower frequencies and is larger in the absolute value (~30 3 40 cm !1 ) [2].In the 31 P NMR spectra, the complexation exerts a weaker effect on the phosphorus chemical shift, compared to the complexation with trialkyl phosphorotrithioites [2,3]. The most significant upfield shift of the P signal upon complexation is observed in IIb: from 112 ...

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“…Earlier we have reported our studies on the coordination properties of thioesters of P(III) acids. The series of complexes of trialkyltrithiophosphites with Cu(I) halides were synthesized, and the structure of most of these complexes in solid state has been studied [16,[18][19][20][21]. It was found that the thiophosphite ligands have significantly different coordination properties as compared with phosphite or amidophosphite ligands.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and crystal structure of some phosphite, thiophosphite, and amidophosphite copper(I) halide complexes

Kursheva¹,

Kataeva²,

Krivolapov³

et al. 2008

Heteroatom Chemistry

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Some Cu(I) halides complexes based on P(III) acid esters,{[(RE)3PCuBr] (where E = O, N, S); R = n‐Pr, i‐Pr, Et2N} were obtained and characterized using IR, 31P NMR spectroscopy, and single crystal X‐ray diffraction. The comparative structural characteristics of complexes with various donor atoms (E = O, N, S) are analyzed. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:483–489, 2008; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20459

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Conformations and coordination properties of trialkyltrithiophosphites in copper(I) complexes

Cited by 16 publications

References 14 publications

The preparation, properties and X-ray structures of gold(I) trithiophosphite complexes

The preparation, properties and X-ray structures of gold(I) trithiophosphite complexes

Synthesis and Structure of Copper(II) Phosphonodithioite Complexes

Synthesis and crystal structure of some phosphite, thiophosphite, and amidophosphite copper(I) halide complexes

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