Structure of crystalline bismuth(III) N,N-dipropyldithiocarbamate [Bi{S2CN(C3H7)2}3] according to 13C and 15N MAS NMR and X-ray diffraction analysis: Supramolecular self-organization and conformational isomerism

Иванов, А. В.; Егорова, И. В.; Иванов, М. А.; Antzutkin, Oleg N.; Tsvykh, R. S.

doi:10.1134/s0012501614010059

Cited by 10 publications

(10 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Along with standard NMR spectroscopic characterization, 15 N NMR spectroscopy can be a valuable tool for the investigation of nitrogen containing compounds. However, such studies on bismuth complexes are extremely rare . We performed 15 N solution NMR spectroscopic experiments on a small series of closely related amido bismuth complexes that differ with respect to the overall complex charge or the donor strength of additional neutral ligands bound to Bi (Scheme and Supporting Information)…”

Section: Resultsmentioning

confidence: 99%

“…However,s uch studies on bismuth complexes are extremely rare. [30] We performed 15 Nsolution NMR spectroscopic experiments on as mall series of closely related amido bismuth complexes that differ with respect to the overall complex chargeo rt he donor strength of additional neutrall igands bound to Bi (Scheme 5a nd Supporting Information). [31] Compound Bi(NiPr 2 ) 3 shows a 15 NN MR chemical shift of À268 ppm.…”

Section: Nnmr Spectroscopymentioning

confidence: 99%

See 1 more Smart Citation

Cationic Bismuth Amides: Accessibility, Structure, and Reactivity

Dengel

Lichtenberg

2016

Chemistry A European J

View full text Add to dashboard Cite

The synthetic access to cationic bismuth compounds based on simple, monodentate, synthetically useful amido ligands, [Bi(NR ) (L) ] , has been investigated (R=Me, iPr, Ph; L=neutral ligand). With [BPh ] as a counteranion, the formation of contact ion pairs and subsequent phenyl transfer from B to Bi is observed. An intermediate of this reaction, [Bi(NMe ) (HNMe )(BPh )] (1), could be isolated and fully characterized. The use of a fluorinated tetraarylborate as a counteranion leads to more stable cationic bismuth amides. The solvent-separated ion pairs [Bi (μ -NMe ) (NMe ) (thf) ] (4) and [Bi(NiPr ) (thf) ] (5) were fully characterized, with [B(3,5-C H (CF ) ) ] anions balancing the positive charge. The coordination chemistry, aggregation in solution, and spectroscopic features of these compounds were investigated. Compounds 4 and 5 show an increased reactivity towards diisopropylcarbodiimide compared to their neutral parent compounds. These reactions result in formation of the first cationic bismuth guanidinates. Characterization techniques include H, B, C, N, F, and P (VT)NMR and IR spectroscopy, single crystal X-ray diffraction analysis, and DFT calculations.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Nnmr Spectroscopymentioning

confidence: 99%

Cationic Bismuth Amides: Accessibility, Structure, and Reactivity

Dengel

Lichtenberg

2016

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…Dithiocarbamates are highly versatile mono-anionic ligands, which can form stable complexes with almost all metals in the periodic table [13]. The metal-dithiocarbamate complexes show a wide structural diversity ranging from mononuclear and binuclear to polymeric supramolecular assemblies [14][15][16], depending on several factors such as the metal centre, alkyl substituents at the nitrogen atom, and also on solvent properties.…”

Section: Introductionmentioning

confidence: 99%

Structural insights into the polymorphism of bismuth(III) di-n-butyldithiocarbamate by X-ray diffraction, solid-state (13C/15N) CP-MAS NMR and DFT calculations

et al. 2017

View full text Add to dashboard Cite

Two crystalline polymorphs of a binuclear tris(di-n-butyldithiocarbamato)bismuth(III) complex, I and II, with an empirical formula of [Bi{S 2 CN(n-C 4 H 9) 2 } 3 ] were synthesised and characterised by X-ray diffraction (XRD), solid-state NMR, and density functional theory (DFT) calculations. At the supramolecular level, these mononuclear molecular units interact in pairs via secondary Bi×××S bonds yielding binuclear formations of [Bi 2 {S 2 CN(n-C 4 H 9) 2 } 6 ]. The polymorph I (!1) contains two isomeric non-centrosymmetric binuclear molecules of [Bi 2 {S 2 CN(n-C 4 H 9) 2 } 6 ], which are related to each other as conformers, therefore, having four structurally inequivalent bismuth atoms and twelve inequivalent dithiocarbamate ligands. In contrast, the structurally simpler polymorph II (!2 $ /&) exists as a single molecular form of the corresponding centrosymmetric binuclear formation comprising two structurally equivalent bismuth atoms and three structurally different dithiocarbamate groups. The polymorphs I and II were found to be interconvertible by altering the solvent system during the recrystallisation process. Sun et al. (2012) has reported a crystalline form of the title compound which resembles, but is not identical with, the polymorph II. Experimental solidstate 13 C and 15 N cross-polarisation (CP) magic-angle-spinning (MAS) NMR spectra of both polymorphs I and II were in accord with the direct structural data on these complexes. Assignments of resonance lines in solid-state 13 C and 15 N NMR spectra assisted by chemical shift calculations of the crystals using periodic DFT.

show abstract

“…Mathematical modeling allowed us to establish inte gral intensity ratio in the group of 13 C signals under discussion (1 : 1 : 2 : 2), which indicates the presence of six nonequivalent PDtc ligands in the structure of compound I. 13 C chemical shifts of =NC(S)S-groups in the range 192.5-201.8 ppm are characterized by systematically lowered values as compared with initial complex Ia (200.1-203.6 ppm) [23]. This difference can be explained by the redistribution of PDtc ligands into the inner sphere of gold(III) with increase in covalent binding strength resulting in the growth of shielding of 13 C nuclei of dithiocarbamate groups.…”

mentioning

confidence: 95%

Preparation, supramolecular self-organization and thermal behavior of polymeric complex of composition ([Au{S2CN(C3H7)2}2]3[Bi3Cl12]) n with unusual geometry of bismuth(III) complex anion

Заева

Иванов

Герасименко

et al. 2015

Russ. J. Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

A reaction of freshly precipitated bismuth(III) N,N dipropyldithiocarbamate (PDtc) with AuCl 3 solution in 2 M HCl was studied. A heteropolynuclear gold(III)-bismuth complex of ionic type [Au{S 2 CN(C 3 H 7 ) 2 } 2 ] 3 [Bi 3 Cl 12 ] (I) was isolated by crystallization of products of the heterogeneous reaction from acetone-chloroform (1 : 1) solution. Crystal and supramolecular structure of compound I established by X ray diffraction study includes structurally nonequivalent complex cations [Au{S 2 CN(C 3 H 7 ) 2 } 2 ] + related to each other as conformers (hereinafter cations A, B, C, and D) in 1 : 1 : 2 : 2 ratio. Due to secondary Au⋅⋅⋅S bonds (3.386-3.617 Å), the isomeric cations form trinuclear species of two types: [C⋅⋅⋅A⋅⋅⋅C] and [D⋅⋅⋅B⋅⋅⋅D] that differ in the character of intercationic binding and Au-Au distances. Relatively weak aurophilic Au⋅⋅⋅Au bonds (3.4704(3) Å) unite the neighboring cationic triads into zigzag polymeric chains of type (⋅⋅⋅[C⋅⋅⋅A⋅⋅⋅C]⋅⋅⋅[D⋅⋅⋅B⋅⋅⋅D]⋅⋅⋅) n oriented along the crystallographic axis b. The spatial isolation of neighboring chains is provided by discrete trinuclear anions [Bi 3 Cl 12 ] 3where metal atoms bind four bridging (μ 2 and μ 3 ) chlorine atoms, while each bismuth atom forms distorted octahedral chromophore [BiCl 6 ]. The complex tri bismuth anion in the structure I is the first example of [Bi 3 Cl 12 ] 3anion of angle rather than linear structure: Bi(1)Bi(2)Bi(3) angle is 72.358°. The thermal behavior of compound I was studied by simultaneous thermal analysis. The multistage process of thermal destruction includes the thermolysis of dithiocarbamate portion of the complex and [Bi 3 Cl 12 ] 3accompanied by reduction of gold(III) to metal and release of BiCl 3 (followed by its evaporation) and partial formation of Bi 2 S 3 . In the temperature range 680-760°C, bismuth sulfide undergoes oxidation to (BiO) 2 SO 4 , which decomposes above 760°C to give Bi 2 O 3 . Residue after thermolysis of compound I is gold metal and bismuth(III) oxide.

show abstract

Structure of crystalline bismuth(III) N,N-dipropyldithiocarbamate [Bi{S2CN(C3H7)2}3] according to 13C and 15N MAS NMR and X-ray diffraction analysis: Supramolecular self-organization and conformational isomerism

Cited by 10 publications

References 14 publications

Cationic Bismuth Amides: Accessibility, Structure, and Reactivity

Cationic Bismuth Amides: Accessibility, Structure, and Reactivity

Structural insights into the polymorphism of bismuth(III) di-n-butyldithiocarbamate by X-ray diffraction, solid-state (13C/15N) CP-MAS NMR and DFT calculations

Preparation, supramolecular self-organization and thermal behavior of polymeric complex of composition ([Au{S2CN(C3H7)2}2]3[Bi3Cl12]) n with unusual geometry of bismuth(III) complex anion

Contact Info

Product

Resources

About