Publisher Summary The chapter presents an overview of the structural diversity demonstrated by complexes of bismuth(III) with organic-based ligands involving the elements of Groups 15 (pnictogens) and 16 (chalcogens) as donor sites, recognizing the potential for tailoring structure and reactivity by manipulation of the organic moiety. Although most complexes of bismuth obey standard valence guidelines, the high and variable coordination numbers accessible to bismuth are responsible for interesting and unpredictable structural arrangements. The formulas of well-defined bismuth compounds are presented to outline the type and extent of characterization data available for each, enabling assessment of the significance and relevance of the observations regarding synthesis and reactivity. Some of the structural features are described in detail to illustrate the novelty or generality of a particular arrangement. A diverse coordination chemistry is emerging for bismuth(III) made possible by a spacious and flexible coordination environment, allowing for coordination numbers in excess of 9.

Coordination complexes of bismuth(III) involving organic ligands with pnictogen or chalcogen donors

General, high-yield metathesis reactions provide two related and comprehensive series of dithiabismuth heterocycles. The compounds are characterized by spectroscopic and X-ray crystallographic analysis. Monocycles 2-chloro-1,3-dithia-2-bismolane (1), 2-chloro-1,3-dithia-2-bismane (2), 2-chloro-1,3-dithia-2-bismepane (3), 2-chloro-1,3,6-trithia-2-bismocane (4), and 2-chloro-1,3-dithia-6-oxa-2-bismocane (5) are kinetically stable with respect to the tethered bicyclic derivatives 1,2-bis((1,3-dithia-2-bismolan-2-yl)thio)ethane (6), 1,3-bis((1,3-dithia-2-bisman-2-yl)thio)propane (7), 1,4-bis((1,3-dithia-2-bismepan-2-yl)thio)butane (8), bis((1,3,6-trithia-2-bismocan-2-yl)thio)ethyl) sulfide (9), and bis(((1,3-dithia-6-oxa-2-bismocan-2-yl)thio)ethyl) ether (10). Mass spectrometry provides an excellent means of characterization of compounds of this nature and is responsible for the identification of monocyclic bismuthenium cations as general and dominant dissociation products. In addition, the atmospheric pressu...

Spectroscopic, structural, and mass spectrometric studies on two systematic series of dithiabismuth(iii) heterocycles : identification of bismuthenium cations and their solvent complexes

Die Darstellung der Titelverbindungen 3 und 4 wird beschrieben. 1H-NMR-, IR-, Raman- und Massenspektren werden zusammen mit den entsprechenden Spektren der analogen Zinnverbindungen 1 und 2 diskutiert. In Losungen der 8-Ringe 1 - 4 besteht ein Gleichgewicht zwischen zwei chiralen Wanne-Sessel-Konformeren uber eine achirale Sessel-Sessel-Konformation. Fur 1 wird ferner eine Berry-Pseudoration am trigonal-bipyramidal koordinierten Sn-Atom angenommen. Versuche zur Darstellung von analogen Si-Verbindungen werden erwahnt.



On Heterocyclic Systems Containing Germanium, I. Synthesis and Investigation of the Eighy-membered Rings 2,2-Dichloro-1,3,6,2-trithiagermocane and 5,5-Dichloro-1,4,6,5-oxadithiagermocane



The synthesis of the title compounds 3 and 4 is described. 1H n.m.r., i.r., Raman, and mass spectra are discussed in relation to the analogous tin compounds 1 and 2. Solutions of the eight-membered rings 1 - 4 contain two chiral boat-chair conformers equilibrized by passing an achiral chair-chair conformation. For 1 a Berry-pseudorotation at the trigonal-bipyramidally coordinated tin atom is further guessed. Experiments for the synthesis of the related silicon compounds are mentioned.

Über Germanium‐haltige Heterocyclen, I. Darstellung und Charakterisierung der 8‐Ring‐Verbindungen 2,2‐Dichlor‐1,3,6,2‐trithiagermocan und 5,5‐Dichlor‐1,4,6,5‐oxadithiagermocan

Die Struktur der Titelsubstanz wurde rontgenographisch aus Diffraktometer-Einkristalldaten bestimmt und bis zu einem konventionellen R von 0,048 verfeinert Der 8-Ring besitzt Wanne-Sessel-Konformation PITZER- und BAEYER-Spannung sind gegenuber Cyclooctan verringert, und an die Stelle der transannularen 1, 5-H…H-Abstosung im Cyclooctan ist eine stabilisierende 1, 5-As…O-Anziehung getreten Die Koordination am As-Atom ist ψ-trigonal-bipyramidal mit axialen Abstanden AsCl 2,27 A, AsO 2,45 A und aquatorialen Abstanden AsS 2,25 A Die Struktur besteht aus 12-fach koordinierten Molekulen



Die Kristalldaten der analogen Sb-Verbindung 5-Chlor-1-oxa-4, 6-dithia-5-stibaocan werden mitgeteilt



On Heterocyclic Systems Containing Arsenic II1) Molecular and Crystal Structure of 5-Chloro-1-oxa-4, 6-dithia-5-arsaocane



The crystal structure of the title compound has been determined from single crystal X-ray data and refined to a conventional R of 0048 The eight-membered ring has the boat-chair conformation PITZER and BAEYER strain are smaller than in cyclooctane and the transannular 1, 5-H…H repulsion in cyclooctane is replaced by a stabilizing 1, 5-As…O attraction The coordination of the As-atom is ψ trigonal-bipyramidal with axial distances AsCl 227 A, AsO 245 A and equatorial distances AsS 225 A The structure consists of 12-coordinated molecules



The crystal data of the analogous Sb compound 5-Chloro-1-oxa-4, 6-dithia-5-stibaocane are given

Über Arsen‐haltige Heterocyclen. II. Molekül‐ und Kristallstruktur von 5‐Chlor‐1‐oxa‐4,6‐dithia‐5‐arsaocan

Die Struktur der Titelsubstanz wurde rontgenographisch aus Diffraktometer-Einkristalldaten bestimmt und bis zu einem konventionellen R von 0,034 verfeinert. Der 8-Ring besitzt Sessel-Sessel-Konformation mit transannularer 1,5- Sn…O-Annaherung. Die Koordination am SnAtom ist trigonal-bipyramidal mit aquatorialen Abstanden SnS 2,369 und SnCl 2,346 A und axialen Abstanden SnO 2,359 und SnCl 2,376 A. Abstandsbereiche fur SnO- und SnS-Bindungen verschiedenen Typs werden festgelegt. Die Struktur besteht aus 12fach koordinierten Molekulen.



On Heterocyclic Systems Containing Tin. II. Molecular and Crystal Structure of 5,5-Dichloro-1-oxa-4,6-dithia-5-stannaocane



The crystal structure of the title compound has been determined from single crystal X-ray data and refined to a conventional R of 0.034. The eight-membered ring has the chair-chair conformation with 1,5-transannular Sn…O-interaction. The coordination of the Snatom is trigonal-bipyramidal with equarorial distances SnS 2.369 and SnCl 2.346 A and axial distances SnO 2.359 and SnCl 2.376 A. Distance ranges for SnO- and SnS-bonds of different types are given. The structure consists of 12-coordinated molecules.

Über Zinn‐haltige Heterocyclen. II. Molekül‐ und Kristallstruktur von 5,5‐Dichlor‐1‐oxa‐4,6‐dithia‐5‐stannaocan

1:1-Komplexe des Bis-(2-mercaptoathyl)-athers wurden durch Reaktion der Metallchloride mit dem Mercaptan in organischen Losungsmitteln erhalten. Die Verbindungen wurden mit chemischen Methoden und durch IR-, 1H-NMR- und Massenspektren charakterisiert.



Bis(2-mercaptoethyl)ether Complexes of As, Sb, Bi, and Sn(IV)



1:1 complexes of bis(2-mercaptoethyl)ether with As, Sb, Bi, and Sn(IV) were synthesized by reaction of the metal chlorides with the mercaptan in organic solvents. The compounds were investigated by different methods.

R. Engler

Papers

Bis‐(2‐mercaptoäthyl)‐äther Komplexe von As, Sb, Bi und Sn(IV)