Synthesis,characterization and cytotoxicity of some triarylbismuth(V) di(N‐p‐toluenesulfonyl) aminoacetates and the crystal structure of (4‐CH3C6H4SO2NHCH2CO2)2Bi(C6H4Cl‐4)3

A series of triarylbismuth(V) di(N‐p‐toluenesulfonyl)aminoacetates with the formula (4‐CH₃C₆H₄SO₂NHCH₂CO₂)₂BiAr₃ (Ar?C₆H₅, 4‐CH₃C₆H₄, 4‐ClC₆H₄, 4‐BrC₆H₄) were synthesized and characterized by elemental analysis, IR, ¹H NMR and mass spectra. The crystal structure of (4‐CH₃C₆H₄SO₂NHCH₂CO₂)₂Bi(C₆H₄Cl‐4)₃ was determined and shows the bismuth to exist in a distorted trigonal bipyramidal geometry. Four human neoplastic cell lines (HL‐60, PC‐3MIE8, BGC‐823 and MDA‐MB‐435) were used to screen these compounds. The results indicate that these compounds at 10 μM show cytotoxicity. Copyright © 2004 John Wiley & Sons, Ltd.     

Triorganoantimon- und Triorganobismutdisulfonate Kristall- und Molekülstrukturen von (C6H5)3M(O3SC6H5)2 (M = Sb,Bi)

Triorganoantimony and Triorganobismuth Disulfonates. Crystal and Molecular Structure of (C₆H₅)₃M(O₃SC₆H₅)₂(M = Sb, Bi) Triorganoantimony disulfonates R₃Sb(O₃SR′)₂ [R = CH₃ = Me, C₆H₅ = Ph; R′ = Me, CH₂CH₂OH, Ph, 4-CH₃C₆H₄. R = Ph; R′ = 2,4-(NO₂)₂C₆H₃], Me₃Sb(O₃SCF₃)₂ · 2 H₂O and triphenylbismuth disulfonates Ph₃Bi(O₃SR′)₂ [R = Me, CF₃, CH₂CH₂OH, Ph, 4-CH₃C₆H₄, 2,4-(NO₂)₂C₆H₃] have been prepared by reaction of Me₃Sb(OH)₂, (Ph₃SbO)₂, and Ph₃BiCO₃, respectively, with the appropriate sulfonic acids. From vibrational data an ionic structure is inferred for Me₃Sb(O₃SCF₃)₂ · 2 H₂O and Me₃Sb(O₃SCH₂CH₂OH)₂, and a covalent structure for the other compounds with a penta-coordinated central atom with trigonal bipyramidal surrounding (Ph or Me in equatorial, unidentate sulfonate ligands in apical positions). Ph₃M(O₃SPh)₂ (M = Sb, Bi) crystallize monoclinic [space group P2₁/c; M = Sb/Bi: a = 1 611.5(8)/1 557.4(9), b = 987.5(6)/1 072,5(8), c = 1 859.9(9)/1 696.5(9) pm, β = 105.71(5)/96.62(5)°; Z = 4; d(calc.) 1.556/1.781 Mg · m^?3; V_cell = 2 849.2 · 10⁶/2 814.8 · 10⁶ pm³; structure determination from 3 438/3 078 independent reflexions (I ≥ 3σ(I)), R(unweighted) = 0.030/0.029]. M is bonding to three Ph groups in the equational plane [mean distances Sb/Bi? C:210.1(4)/219.1(7) pm] and two sulfonate ligands with O in apical positions [distances Sb? O: 210.6(3), 212.8(2); Bi? O: 227.6(5), 228.0(4) pm]. Weak interaction of M with a second O atom of one sulfonate ligand is inferred from a rather short M? O contact distance [Sb? O: 327.4(4), Bi? O: 312.9(5) pm], and from the distortion of equatorial angles [C? Sb? C: 128.4(2), 119.2(2), 112.2(2); C? Bi? C: 135.9(3), 117.8(3), 106.3(3)°]     

Schwermetall-π-Komplexe. IX. Die Kettenpolymere [(1,2- (CH3)2C6H4BiCl3)2], [(1,3) (CH3)2C6H4BiCl3)2] und [(1,4- (CH3)2C6H4BiCl3)2]

Heavy Metal π-Complexes. IX. The Chain Polymers [(1,2- (CH₃)₂C₆H₄BiCl₃)₂], [(1,3- (CH₃)₂C₆H₄BiCl₃)₂] and [(1,4- (CH₃)₂C₆H₄BiCl₃)₂] In the crystal structures of the three solid state complexes (C₆H₄(CH₃)₂BiCl₃ (C₆H₄(CH₃)₂ = o-xylene: 1 , m-xylene: 2 , p-xylene: 3 ) quasi-dimeric units of almost undistorted, arene coordinated BiCl₃ fragments can be found that are further associated via additional Bi? Cl contacts to form one-dimensional polymeric chains. Whereas the chains of 2 and 3 are constituted by Bi₂Cl₂ four-membered rings only, further Cl-bridging in 1 leads to additional trigonal-bipyramidal arrangements with Bi atoms exhibiting coordination numbers of 3 + 3 + 1 and 3 + 2 + 1, respectively (prim. + sec. Cl contacts + arene). The arene-metal bonding is characterized by Bi-arene distances in the range from 297 – 306 pm, including ring slippages of 24 –41 pm and 73 pm with the Bi atoms being six and seven coordinated, respectively. The direction of this slipping with respect to the arene's methylation sites cannot be understood in terms of electronic influences but is shown to be caused by steric demands. The values IP₁ of the arenes prove to determine the colours of the complexes.     

Syntheses and Spectroscopic Study of Some New N‐4‐Fluorobenzoyl Phosphoric Triamides; Crystal Structures of 4‐F‐C6H4C(O)N(H)P(O)R2, R = NH‐C(CH3)3, NH‐CH2C6H5, N(CH3)(CH2C6H5)

Some new N‐4‐Fluorobenzoyl phosphoric triamides with formula 4‐F‐C₆H₄C(O)N(H)P(O)X₂, X = NH‐C(CH₃)₃ ( 1 ), NH‐CH₂‐CH=CH₂ ( 2 ), NH‐CH₂C₆H₅ ( 3 ), N(CH₃)(C₆H₅) ( 4 ), NH‐CH(CH₃)(C₆H₅) ( 5 ) were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR and Mass spectroscopy and elemental analysis. The structures of compounds 1 , 3 and 4 were investigated by X‐ray crystallography. The P=O and C=O bonds in these compounds are anti. Compounds 1 and 3 form one dimensional polymeric chain produced by intra‐ and intermolecular ‐P=O···H‐N‐ hydrogen bonds. Compound 4 forms only a centrosymmetric dimer in the crystalline lattice via two equal ‐P=O···H‐N‐ hydrogen bonds. ¹H and ¹³C NMR spectra show two series of signals for the two amine groups in compound 1 . This is also observed for the two α‐methylbenzylamine groups in 5 due to the presence of chiral carbon atom in molecule. ¹³C NMR spectrum of compound 4 shows that ²J(P,C_aliphatic) coupling constant for CH₂ group is greater than for CH₃ in agreement with our previous study. Mass spectra of compounds 1 ‐ 3 (containing 4‐F‐C₆H₄C(O)N(H)P(O) moiety) indicate the fragments of amidophosphoric acid and 4‐F‐C₆H₄CN⁺ that formed in a pseudo McLafferty rearrangement pathway. Also, the fragments of aliphatic amines have high intensity in mass spectra.     

Triorganoantimon- und Triorganobismutderivate von Carbonsäuren fünfgliedriger Heterocyclen Kristall- und Molekülstruktur von (C6H5)3Sb(O2C-2-C4H3S)2

Inhaltsübersicht. Triorganoantimon- und Triorganobismutdicarboxylate R₃M[O₂C(CH₂)ⁿ-2-C₄H₃X]₂ (M = Sb, R = CH₃, C₆H₁₁, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄; n = 0, X = O, S, NH, NCH₃. M = Sb, R = CH₃, C₆H₅; M = Bi, R = C₆H₅; n = 1, X = O, S. M = Sb, R = C₆H₁₁, n = 1, X = S; R = 4-FC₆H₄, n = 0, X = O, S, NCH₃; R = 2,4,6-(CH₃)₃C₆H₂, n = 0, X = O, S, NH) wurden durch Reaktionen von R₃Sb(OH)₂ (R = CH₃, C₆H₁₁, 2,4,6-(CH₃)₃C₆H₂), R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄, 4-FC₆H₄) bzw. R₃BiCO₃ mit den entsprechenden fünfgliedrigen heterocyclischen Carbonsäuren 2-C₄H₃X(CH₂)_nCOOH dargestellt. Auf der Basis schwingungsspektroskopischer Daten wird für alle Verbindungen eine trigonal bipyramidale Umgebung vom M (zwei O-Atome von einzähnigen Carboxylatliganden in den apikalen, drei C-Atome von R in den äquatorialen Positionen) vorgeschlagen, ferner eine schwache Wechselwirkung zwischen O(=C) jeder Carboxylatgruppe und M. Die Kristallstrukturbestimmung von (C₆H₅)₃Sb(O₂C–2-C₄H₃S)₃ stützt diesen Vorschlag. Die Verbindung kristallisiert triklin [Raumgruppe P$1; a = 891,8(14), b = 1058,2(12), c = 1435,6(9) pm, α = 68,53(8), β = 85,47(9), γ = 85,99(11)°; Z = 2; d(ber.) = 1,607 Mg m^–3; V(Zelle) = 1255,6 ų; Strukturbestimmung anhand von 3947 unabhängigen Reflexen (F_o > 3σ(F²_o)), R(ungewichtet) = 0,037]. Sb bindet drei C₆H₅-Gruppen in der äquatorialen Ebene [mittlerer Abstand Sb–C: 211,1(5)pm] und zwei einzähnige Carboxylatliganden in den apikalen Positionen einer verzerrten trigonalen Bipyramide [mittlerer Abstand Sb–O: 212,0(4) pm]. Aus den relativ kurzen Sb – O(=C)-Abständen [274,4(4) und 294,9(4) pm] und aus der Aufweitung des dem O(=C)-Atom nächsten äquatorialen C–Sb–C-Winkels auf 145,9(2)° [andere C-Sb-C-Winkel: 104,4(2), 109,5(2)°] wird auf schwache Sb–O(=C)-Koordination geschlossen. Schließlich wird eine Korrelation zwischen dem (+, –)I-Effekt des Organoliganden R an M (M = Sb, Bi) und der Stärke der M–O(=C)-Koordination in den Dicarboxylaten R₃M[O₂C(CH₂)_n–2-C₄H₃X]₂ vorgeschlagen. Triorganoanümony and Triorganobismuth Derivatives of Carbonic Acids of Five-membered Heterocycles. Crystal and Molecular Structure of (C₆H₅)₃Sb(O₂C–2-C₄H₃S)₂ Triorganoantimony- and triorganobismuth dicarboxylates R₃M[O₂C(CH₂)_n–2-C₄H₃X]₂ (M = Sb, R = CH₃, C₆H₁₁, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄; n = 0, X = O, S, NH, NCH₃. M = Sb, R = CH₃, C₆H₅; M = Bi, R = C₆H₅; n = 1, X = O, S. M = Sb, R = C₆H₁₁, n = 1, X = S; R = 4-FC₆H₄, n = 0, X = O, S, NCH₃; R = 2,4,6-(CH₃)₃C₆H₂, n = 0, X = O, S, NH) have been prepared by reaction of R₃Sb(OH)₂ (R = CH₃, C₆H₁₁; 2,4,6-(CH₃)₃C₆H₂), R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄, 4-FC₆H₄) or R₃BiCO₃ with the appropriate five-membered heterocyclic carboxylic acid. From vibrational data for all compounds a trigonal bipyramidal environment around M (two O atoms of unidendate carboxylate ligands in apical, three C atoms (of R) in equatorial positions) is proposed and also an additional weak interaction of O(=C) of each carboxylate group and M. The crystal structure determination of Ph₃Sb(O₂C–2-C₄H₃S)₂ gives additional prove to this proposal. It crystallizes triclinic [space group P$1; a = 891.8(14), b = 1058.2(12), c = 1435.6(9) pm, α = 68.53(8), β = 85.47(9), γ = 85.99(11)°; Z = 2; d(calc.) = 1.607 Mg m^–3; V_cell = 1255.6 ų; structure determination from 3 947 independent reflexions (F_o > 3σ(F²_o)), R(unweighted) = 0.037]. Sb is bonding to three C₆H₅ groups in the equatorial plane [mean distance Sb–C: 211.1(5) pm] and two unidentate carboxylate ligands in the apical positions of a distorted trigonal bipyramid [mean distance Sb–O: 212.0(4) pm]. From the relatively short Sb–O(=C) distances [274.4(4) and 294.9(4) pm] and from the enlarged value of the equatorial C–Sb–C angle next to the O(=C) atom [145.9(2)°; other C–Sb–C angles: 104.4(2), 109.5(2)°] additional weak Sb–O(=C) coordination is inferred. Finally a correlation between the (+, –) I-effect of the organic ligands It at M and the strength of the M–O = C interaction is suggested.     

Titrimetric determination of microgram amounts of bismuth by thiocyanate amplification after precipitation as Bi(SCN)6[N(C4H9)4]3

Bismuth (15–90 μg) is precipitated as Bi(SCN)₆[N(C₄H₉)₄]₃. After filtration, the precipitate is treated with hydrogencarbonate solution and the thiocyanate released is determined by a titrimetric procedure which provides 228 iodine atoms for each original bismuth ion.     

Synthesis,characterization and in vitro antitumor activity of some arylantimony ferrocenecarboxylates and crystal structures of C5H5FeC5H4CO2SbPh4 and (C5H5FeC5H4CO2)2Sb(4‐CH3C6H4)3

A series of arylantimony ferrocenecarboxylates with the formula (C₅H₅FeC₅H₄CO₂)_nSbAr_(5?n) (n = 1, 2; Ar = C₆H₅, 4‐CH₃C₆H₄, 3‐CH₃C₆H₄, 2‐CH₃C₆H₄, 4‐ClC₆H₄, 4‐FC₆H₄) were synthesized and characterized by elemental analysis, IR, ¹H NMR and mass spectra. The crystal structures of (C₅H₅FeC₅H₄CO₂)₂Sb(4‐CH₃C₆H₄)₃ and C₅H₅FeC₅H₄CO₂SbPh₄ were determined by X‐ray diffraction. Four human neoplastic cell lines (HL‐60, Bel‐7402, KB and Hela) were used to screen these compounds. The results indicate that these compounds at 10 µM show certain in vitro antitumor activities. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis and x-ray structural investigation of bismuth 2-methyl-8-quinolineselenolate Bi[C<Subscript>9</Subscript>H<Subscript>5</Subscript>(CH<Subscript>3</Subscript>)NSe]<Subscript>3</Subscript>

Bismuth 2-methyl-8-quinolineselenolate, Bi[C₉H₅(CH₃)NSe]₃, was synthesized. X-ray analysis was used to determine the structure of this complex. The crystal chemistry of bismuth(III), antimony(III), and arsenic(III) 2-methyl-8-quinolineselenolates and 2-methyl-8-quinolinethiolates was discussed relative to the effect of going from Se to S as the ligand atoms and presence of a methyl group at C-2 of the quinoline system and unshared electron pair of the central atom in the complex.     

铋(Ⅲ)配合物Bi(1,10-phen)[S2CN(CH3)2]2(NO3),

Three bismuth（Ⅲ） complexes Bi（1,10-phen）[S2CN（CH3）2]2（NO3） （1）, {Bi（S2COCH3）[S2CNC6Hs（CH3）]2}2 （2） and [Bi（S2CNBu2）2（CH3OH）（NO3）]∞ （3） were synthesized and characterized by elemental analysis and IR spectra. Their crystal structures were determined by X-ray single crystal diffraction analysis. Studies show that complex 1 has a monomeric structure with the central bismuth atom eight-coordinated in a capped distorted pentagonal bipyramidal geometry. The complex 2 takes centrosymmetric dimeric structure and the bismuth atoms are seven-coordinated in distorted pentagonal bipyramidal geometry.In complex 3, the bismuth atoms are seven-coordinated in distorted pentagonal bipyramidal geometry by bridging nitrate O atoms and the resulting structure is onedimensional infinite chain polymer.     

Protonation of the metal—metal bond in Fe2(μ-A)(μ-A′)(CO)4L2 complexes (A  A′ SC6H5, P(C6H5)2, P(CH3)2; A  SC6H5, A′ z.dbnd; P(C6H5)2; L z.dbnd; P(C6H5)3-n(CH3)n). : III. Experimental study of the influence of the A and A′ bridges on the basicity of the metal—metal bond

In order to check the influence of the bridges on the basicity of the metal—metal bond in Fe₂(μ-A)(μ-A′)(CO)₄L₂ complexes, the compounds with A  A′ SC₆H₅, P(C₆H₅)₂; P(CH₃)₂; A  SC₅H₅, A′ P(C₆H₅)₂ and L  P(CH₃)_3-n (C₆H₅)_n (n  0—3) have been prepared. IR and PMR spectroscopic results are interpreted in structural terms, and show that the Fe₂(SC₆H₅)(P(C₆H₅)₂.)-(CO)₄L₂ complexes are non rigid on the NMR time scale for n = 0, 1. Replacement of the first SC₆H₅ bridge by a P(C₆H₅)₂ bridge markedly increase the basicity of the metal—metal bond, but replacement of the second SC₆H₅ bridge has no significant effect.     

Synthese und Strukturen neuer Ringverbindungen des Bismuts mit Tris(trimethylsilyl)silyl und ‐stannylresten – [(Me3Si)3Si]4Bi4 und [(Me3Si)3Sn]6Bi8

Synthesis and Structures of Novel Ring Compounds of Bismuth with Tris(trimethylsilyl)silyl and ‐stannyl Substituents – [(Me₃Si)₃Si]₄Bi₄ and [(Me₃Si)₃Sn]₆Bi₈ A bicyclo[3.3.0]octane‐like core consisting of eight bismuth atoms is found in the novel octabismuthane Bi₈[Sn(SiMe₃)₃]₆. It is prepared like Bi₄[Si(SiMe₃)₃]₄ by reduction of BiBr₃ with Li(thf)₃E(SiMe₃)₃ (E = Si, Sn) together with (Me₃Si)₆E₂. Both bismuth ring compounds have been characterized by single crystal X‐ray crystallography.     

Untersuchungen an Selen-Verbindungen. LXIV. Darstellung und Eigenschaften von Säurederivaten von Phenylselen(IV) -Verbindungen (C6Hs) 2SeX2, (C6H5) 3SeX

Studies on Selenium Compounds. LXIV. Preparation and Properties of Acid Derivatives of Phenylselenium(IV) Compounds (C₆H₅) ₂SeX₂ and (C₆H₅) ₃SeX. Reactions of (C₆H₅) ₂SeBr₂ and (C₆H₅) ₃SeCl with silver salts of acids are investigated. From (C₆H₅) ₂SeBr₃ and AgY (Y = N0₃, CH₃CO₃, CF₃CO₂, 1/2 SO₄, CH₃SO₃, NCO) the compounds (C₆H₅) ₂Se(NO₃) ₂ (C₆H₅) ₂Se(CH₃CO₂) ₂, (C₆H_s) ₂Se(CF₃CO₂) ₂, (C₆H₅) ₂SeSO₄, (C₆H₅) ₂Se(CH₃SO₃) ₂ and (C₆H₅) ₂Se(NCO) ₂ are prepared. They are characterized by solubility, molecular weight and conductivity. Reaction of (C₆H₅) ₃SeCl and AgX (X = NO₃, CH₃CO₂) yields (C₆H₅) ₃SeNO₃ and (C₆H₅) ₃SeCH₃CO₂.     

Reaktionen eines Dibismutans und von Cyclobismutanen mit Metallcarbonylen ‐ Synthesen von Komplexen mit R2Bi‐, RBi‐, Bi2‐ und Bin‐Liganden (R = Me3CCH2, Me3SiCH2)

Reactions of a Dibismuthane and of Cyclobismuthanes with Metal Carbonyls ‐ Syntheses of Complexes with R₂Bi‐, RBi‐, Bi₂‐ and Bi_n‐ligands (R = Me₃CCH₂, Me₃SiCH₂) Reactions of [Fe₂(CO)₉] with [(Me₃CCH₂)₄Bi]₂ or cyclo‐(Me₃SiCH₂Bi)_n (n = 3 ‐ 5) lead to the complexes [(R₂Bi)₂Fe(CO)₄], [RBiFe(CO)₄]₂[R = Me₃CCH₂, Me₃SiCH₂] and [Bi₂Fe₃(CO)₉]. [Bi₂{Mn(CO)₂C₅H₄CH₃}₃] forms in a photochemical reaction of [Mn(CO)₃C₅H₄CH₃] with cyclo‐(Me₃SiCH₂Bi)_n.     

Ein anionischer Oxohydroxo‐Komplex mit Bismut(III): Na6[Bi2O2(OH)6](OH)2 · 4H2O

An Anionic Oxohydroxo Complex with Bismuth(III): Na₆[Bi₂O₂(OH)₆](OH)₂ · 4H₂O Colourless, plate‐like, air sensitive crystals of Na₆[Bi₂O₂(OH)₆](OH)₂ · 4H₂O are obtained by reaction of Bi₂O₃ or Bi(NO₃)₃ · 5H₂O in conc. NaOH (58 wt %) at 200 °C followed by slow cooling to room temperature. The crystal structure (triclinic, P 1¯, a = 684.0(2), b = 759.8(2), c = 822.7(2) pm, α = 92.45(3)°, ß = 90.40(3)°, γ = 115.60(2)°, Z = 1, R1, wR2 (all data), 0, 042, 0, 076) contains dimeric, anionic complexes [Bi₂O₂(OH)₆]^4— with bismuth in an ψ¹‐octahedral coordination of two oxo‐ and three hydroxo‐ligands. The thermal decomposition was investigated by DSC/TG or DTA/TG and high temperature X‐ray powder diffraction measurements. In the final of three steps the decomposition product is Na₃BiO₃.     

2J(P,C) and 3J(P,C) Coupling Constants in Some New Phosphoramidates. Crystal Structures of CF3C(O)N(H)P(O)[N(CH3)(CH2C6H5)]2 and 4‐NO2‐C6H4N(H)P(O)[4‐CH3‐NC5H9]2

Some new phosphoramidates were synthesized and characterized by ¹H, ¹³C, ³¹P NMR, IR spectroscopy and elemental analysis. The structures of CF₃C(O)N(H)P(O)[N(CH₃)(CH₂C₆H₅)]₂ ( 1 ) and 4‐NO₂‐C₆H₄N(H)P(O)[4‐CH₃‐NC₅H₉]₂ ( 6 ) were confirmed by X‐ray single crystal determination. Compound 1 forms a centrosymmetric dimer and compound 6 forms a polymeric zigzag chain, both via ‐N‐H…O=P‐ intermolecular hydrogen bonds. Also, weak C‐H…F and C‐H…O hydrogen bonds were observed in compounds 1 and 6 , respectively. ¹³C NMR spectra were used for study of ²J(P,C) and ³J(P,C) coupling constants that were showed in the molecules containing N(C₂H₅)₂ and N(C₂H₅)(CH₂C₆H₅) moieties, ²J(P,C)>³J(P,C). A contrast result was obtained for the compounds involving a five‐membered ring aliphatic amine group, NC₄H₈. ²J(P,C) for N(C₂H₅)₂ moiety and in NC₄H₈ are nearly the same, but ³J(P, C) values are larger than those in molecules with a pyrrolidinyl ring. This comparison was done for compounds with six and seven‐membered ring amine groups. In compounds with formula XP(O)[N(CH₂R)(CH₂C₆H₅)]₂, ²J(P,CH₂)_benzylic>²J(P,CH₂)_aliphatic, in an agreement with our previous study.     

Triorganoantimon- und Triorganobismutderivate von 2-Pyridincarbonsäure und 2-Pyridylessigsäure Kristall- und Molekülstrukturen von (C6H5)3Sb(O2C-2-C5H4N)2 und (CH3)3Sb(O2CCH2-2-C5H4N)2

Triorganoantimony and Triorganobismuth Derivatives of 2-Pyridinecarboxylic Acid and 2-Pyridylacetic Acid. Crystal and Molecular Structures of (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ Triorganoantimony and triorganobismuth dicarboxylates R₃M(O₂C-2-C₅H₄N)₂ (M = Sb, R = CH₃, C₆H₅, 4-CH₃OC₆H₄; M = Bi, R = C₆H₅, 4-CH₃C₆H₄) and (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ have been prepared from (CH₃)₃Sb(OH)₂, R₃SbO (R = C₆H₅, 4-CH₃OC₆H₄), or R₃BiCO₃ (R = C₆H₅, 4-CH₃C₆H₄) and the appropriate heterocyclic carboxylic acid. Vibrational spectroscopic data indicate a trigonal bipyramidal environment of M the O(? C)-atoms of the carboxylate ligands being in the apical and three C atoms (of R) in the equatorial positions; in addition coordinative interaction occurs in the 2-pyridinecarboxylates between M and O(?C) of one and N of the other carboxylate ligand and in (CH₃)₃)Sb(O₂CCH₂-2-C₅H₄N)₂ between Sb and O(?C) of both carboxylate ligands. (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂/(CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂ crystallize monoclinic [space group P2₁/c/P2₁/n; a = 892.6(9)/1043.4(6), b = 1326.9(6)/3166.2(18), c = 2233.1(9)/1147.5(7) pm, β = 99.74(8)°/97.67(5)° Z = 4/8; d(calc.) = 1.522/1.553 × Mg m^?3; V_cell = 2606.7 × 10⁶/3757.0 × 10⁶pm³, structure determination from 3798/4965 independent reflexions (F ≥ 4.0 σ(F))/(I ≥ 1.96 σ(I), R(unweighted) = 0.024/0.036]. Sb is bonding to three C₆H₅/CH₃ groups in the equatorial plane [mean distances Sb? C: 212.2(3)/208.7(6) pm] and two carboxylate ligands via O in the apical positions [Sb? O distances: 218.5(2), 209.9(2)/212.1(3), 213.2(3) pm]. In (C₆H₅)₃Sb(O₂C-2-C₅H₄N)₂ there is a short Sb? O(?C) and a short Sb? N contact [Sb? O: 272.1(2), Sb? N: 260.2(2) pm] and distoritions of the equatorial angles [C? Sb? C: 99.2(1)°, 158.2(1)°, 102.0(1).] and of the axial angle [O? Sb? O: 169.9(1)°], and in (CH₃)₃Sb(O₂CCH₂-2-C₅H₄N)₂, which contains two different molecules in the asym-metric unit, there are two Sb? O(?C) contacts [Sb? O, mean: 302.2(4), and 310.7(4)pm, respectively] and distortions of the equatorial angles [C? Sb? C: 114.5(2)°, 132.4(3)° 113.1(2)°, and 123.9(3)° 115.5(2)°, 120.6(3)°, respectively] and of the axial angles [O? Sb? O: 174,9(1)°, 177.9(1)°, respectively].     

Darstellung und NMR-spektroskopische Untersuchungen der tert-Butylimino-cyclopentadienylvanadium (V)-Verbindungen tC4H9NVCpX2 (X=SR,SeC6H5, Br,I)

Synthesis and NMR Spectroscopic Studies of tert-Butylimino-cyclopentadienylvanadium(V) Compounds ^tC₄H₉N?VCpX₂ (X=SR, SeC₆H₅, Br, I ) Syntheses of the cyclopentadienylvanadium(V) compounds ^tC₄H₉N?VCpX₂ (X=SR, SeC₆H₅, Br, I) ^tC₄H₉N?VCp (S^tC₄H₉) and ^tC₄H₉N?VCp[S? (CH₂)₃? S] ( 4 ) are described starting from ^tC₄H₉N?VCpCl₂. ^tC₄H₉N?VCl₃ reacts with BBr₃ and BI₃ by halogen exchange forming the trihalogenides ^tC₄H₉N?VX₃ (X=Br, I). All compounds obtained are characterized by ¹H and ⁵¹V NMR spectroscopy. 4 has been found by X-ray diffraction analysis to be a distorted tetrahedral vanadium complex with a chair conformation of the VS₂C₃-ring.     

Beiträge zur Chemie des Phosphors. 67. Zur Kenntnis der Cyclotriphosphane (PC6H5)3, (PC6H5)2(PC2H5) und (PC6H5)2(PCH3)

Contributions to the Chemistry of Phosphorus. 67. About the Cyclotriphosphanes (PC₆H₅)₃, (PC₆H₅)₂(PC₂H₅), and (PC₆H₅)₂(PCH₃) The reaction of (CH₃)₃Si(C₆H₅)P? P(C₆H₅)Si(CH₃)₃ with RPCl₂ (R = C₆H₅, C₂H₅, CH₃) yields the cyclotriphosphanes (PC₆H₅)₃ 1 , (PC₆H₅)₂(PC₂H₅) 3 , and (PC₆H₅)₂(PCH₃) 4 , respectively. Besides, the corresponding homo- and mixed-substituted cyclotetraphosphanes, cyclopentaphosphanes, and cyclohexaphosphanes are formed. The relative concentrations of the cyclotriphosphanes in the reaction mixtures decrease continuously, whereas those of the cyclopentaphosphanes increase. The reasons for these ring-interconversion reactions of the cyclophosphanes (PR)_n are discussed. The cyclotriphosphanes 1, 3 , and 4 are characterized by ³¹P chemical shifts between +130 and +160 ppm that are at considerable high field compared to open-chain triphosphanes and cyclophosphanes of different ring-size. The substituents R are situated on both sides of the P₃-ring plane, thus giving rise to two diastereomers of 3 that are observed simultaneously in the statistically expected ratio. The ³¹P n.m.r. parameters of 1 and 3 are reported and discussed.     

(Carbonyl)Iron‐Selenolates: New Synthetic Methods and Reactions with Electrophiles. Crystal Structures of [(CO)6Fe2(μ‐SeR)2]; R = Me3SiCH2 and p‐O2NC6H4CH2, {(CO)6Fe2[μ‐η2‐Se,Se′‐o‐(SeCH2C6H4CH2Se)]}, and [(CO)6Fe2(μ‐SeFe(CO)2cp)2]

The reactions of Fe(CO)₅ or Fe₃(CO)₁₂ with NaBEt₃H or KB[CH(CH₃)C₂H₅]₃H, respectively and treatment of the resulting carbonylates M₂Fe(CO)₄, M = Na, K with elemental selenium in appropriate ratios lead to the formation of M₂[Fe₂(CO)₆(μ‐Se)₂]. Subsequent reactions with organo halides or the complex fragment cpFe(CO)₂⁺, cp = η⁵‐C₅H₅ afforded the selenolato complexes [Fe₂(CO)₆(μ‐SeR)₂], R = CH₂SiMe₃ ( 1 ), CH₂Ph ( 2 ), p‐CH₂C₆H₄NO₂ ( 3 ), o‐CH₂C₆H₄CH₂ ( 4 ) and cpFe(CO)₂⁺ ( 5 ) in moderate to good yields. A similar reaction employing Ru₃(CO)₁₂, Se and p‐O₂NC₆H₄CH₂Br leads to the formation of the corresponding organic diselenide. The X‐ray structures of 1 , 3 , 4 and 5 were determined and revealed butterfly structures of the Fe₂Se₂ cores. The substituents in 1 , 3  and 5 adopt different conformations depending on their steric demand. In 4 , the conformation is fixed because of the chelate effect of the ligand. The Fe–Se bond lengths lie in the range 235 to 240 pm, with corresponding Fe–Fe bond lengths of 254 to 256 pm. The ⁷⁷Se NMR data of the new complexes are discussed and compared with the corresponding data of related complexes.     

Dimeric Structure of [(η2‐NO3)2(tpy)Bi(μ‐OH)2Bi(tpy)(η2‐NO3)2]

The synthesis and single crystal X‐ray structure determination are reported for the 2,2′ : 6′,2″‐terpyridine (= tpy) adduct of bismuth(III) nitrate. The hydroxide‐bridged dimer [(η²‐NO₃)₂(tpy)Bi(μ‐OH)₂Bi(tpy)(η²‐NO₃)₂] with nine‐coordinate geometry about Bi was the only isolable product from all crystallization attempts in varying ratios of Bi(NO₃) : terpy.; [(η²‐NO₃)₂(tpy)Bi(μ‐OH)₂Bi(tpy) · (η²‐NO₃)₂] is triclinic, P 1, a = 7.941(8), b = 10.732(9), c = 11.235(9) Å; α = 63.05(1), β = 85.01(1), γ = 79.26(1)°, Z = 1, dimer, R = 0.058 for N₀ = 2319.