13241-47-9Relevant academic research and scientific papers
Germanium-containing ferrocenes and ferrocenophanes. Potential precursors for ring-opening polymerizations and 'germaferrocenes'
Zürcher, Stefan,Gramlich, Volker,Togni, Antonio
, p. 355 - 364 (1999)
The new germanium-containing ferrocene and ferrocenophane derivatives (2,3,4,5-tetramethylbuta-1,3-dien-1,4-diyl)-germa-[1]ferrocenophane (2), 2-(2,3,4,5-tetramethylbuta-1,3-dien-1,4-diyl)-1,3-dithia-2-germa-[3] ferrocenophane (3), 1,1′-bis(1-ethoxy-2,3,4,5-tetramethyl-1-germacyclopenta-2,4-dienyl)- ferrocene (6), 1,3-bis(2,3,4,5-tetramethylbuta-1,3-dien-1,4-diyl)-1,3-digerma-2-oxo-[3] ferrocenophane (7), 1,1′-bis(1-hydrido-2,3,4,5-tetramethyl-1-germacyclopenta-2,4-dienyl)- ferrocene (8) and 1,2-bis(2,3,4,5-tetramethylbuta-1,3-dien-1,4-diyl)-digerma-[2]ferrocenophane (9) have been prepared starting from the dichlorogermol 1. The synthesis of the known ferrocenophanes dichloro-(ferrocene-1,1′-dithiolato)-germane (10a) and dichloro-(ferrocene-1,1′-dithiolato)-stannane (10b) was improved. X-ray crystal structural studies of 2 (C18H20FeGe, a=10.907(4), b=11.040(4), c=13.771(5) ?, β=110.87°, monoclinic, C2/c (No. 15), Z=4), 3 (C18H20FeGeS2, a=8.104(3), b=8.593(4), c=13.177(6) ?, α=70.79(4), β=77.56(3), γ=85.80(3) ? triclinic, P1? (No. 2), Z=2), 7 (C26H32FeGe2O, a=18.95(2), b=8.557(6), c=16.69(6) ?, β=110.65(6)°, monoclinic, C2/c (No. 15), Z=4), 9 (C26H32FeGe2, a=11.209(6), b=10.839(5), c=19.819(10) ?, β=92.89(2), γ=90°, monoclinic, P21/n (No. 14), Z=4), 10a (C10H8FeGeS2, a=10.873(5), b=7.417(4), c=16.415(10) ?, orthorhombic, Pca21 (No. 29), Z=4), 12a (C20H16Fe2GeS4, a=7.459(4), b=10.921(5), c=23.552(12) ?, orthorhombic, Pbcn (No. 60), Z=4) and 12b (C20H16Fe2SnS4, a=7.484(4), b=10.953(6), c=23.917(12) ?, orthorhombic, Pbcn (No. 60), Z=4) and cyclovoltammetric characterizations for all ferrocene-containing compounds have been carried out.
Synthesis and characterization of novel penta- and hexacoordinated sulfur-containing spirocyclic tin(IV) complexes
Sau, Arjun C.,Holmes, Robert R.,Molloy, Kieran C.,Zuckerman
, p. 1421 - 1427 (2008/10/08)
Reactions of bis(toluene-3,4-dithiolato)tin(IV), Sn(TDT)2 (2), with the bases dimethyl sulfoxide (Me2SO), hexamethylphosphoramide (HMPA), and triphenylphosphine oxide (Ph3PO) yield hexacoordinated spirocyclic neutral adducts. Hydroxide ion with 2 gives a hexacoordinated dianionic product. Various reactions of 2 with a variety of halide salts yield new spirocyclic pentacoordinated monoanionic compounds, [XSn(TDT)2]-[R4M]+ (M = N, P, As). Large cations tend to stabilize the complexes. Reversible color changes take place on heating the pentacoordinated derivatives. The substances are characterized by 1H NMR and tin-119m M?ssbauer spectroscopy. The isomer shift of the monohalo anions shows a decrease with halogen electronegativity consistent with electron withdrawal at the tin center. The quadrupole splitting (QS) values are in the range 1.06-1.44 mm s-1 for the pentacoordinated monoanions investigated. These low values, lower than many QS values for tetracoordinate tin(IV) compounds, are associated with rectangular-pyramidal geometries around tin, as found by X-ray diffraction studies on representative members.
A new geometrical form for tin. Synthesis and structure of the spirocyclic complex [(CH3)4N][(C7H6S2) 2SnCl] and the related monocyclic derivative [(C2H5)4N][(C7H6S 2)Ph2SnCl]
Sau, Arjun C.,Day, Roberta O.,Holmes, Robert R.
, p. 3076 - 3081 (2008/10/08)
The synthesis and X-ray structure of the tetramethylammonium chloride adduct of the spirobi(dithiolato)stannate(IV), [(CH3)4N]+[(C7H6S 2)2SnCl]-, (2), provide the first example of a tin compound having a discrete rectangular-pyramidal geometry. The synthesis and X-ray structure of the related monocyclic derivative [(C2H5)4N]+[(C7H 6S2)Ph2SnCl]- (4) shows tin to possess a trigonal-bipyramidal geometry. 2 crystallizes in the monoclinic space group Cc, with a = 14.126 (4), b = 11.485 (6) ?, c = 14.609 (5) ?, β = 100.37 (3)°, and Z = 4. 4 crystallizes in the monoclinic space group P21/c, with a = 12.344 (4) ?, b = 11.975 (5) ?, c = 19.120 (5) ?, β = 96.41 (2)°, and Z = 4. Data for both compounds were collected on an Enraf-Nonius CAD 4 automated diffractometer out to a maximum 2θMo Kα of 50°. The final conventional unweighted residuals were 0.039 and 0.048 for 2 and 4, respectively. It is shown that the 119mSn M?ssbauer quadrupole splitting parameter is useful in distinguishing the square (or rectangular) pyramid from the trigonal bipyramid. Comparison of pentacoordinated tin(IV) with pentacoordinated germanium(IV) and phosphorus shows that the known rectangular pyramids have spirocyclic systems as a common structural feature.
