A series of 13 2,2-difunctional triorganotin chlorides of the general formula Me2(Cl)SnCH2CH(XO)YO(XO, YO P(O)R2, C(O)R; R  OiPr, OEt, Ph) has been synthesized by chlorination of the corresponding tetraorganotin compounds Me3SnCH2CH(XO)YO with HCl in diethyl ether. The crystal structure determination of Me2(Cl)SnCH2CH[P(O)(OiPr)2]2 (VIII), IR spectroscopic data and NMR studies reveal, for the title compounds, molecular structures in which the tin atom, approaches a trigonal-bipyramidal pentacoordinated ligand arrangement as result of an intramolecular Sn … O interaction of one of the two functional groups XO or YO respectively. In solution the compounds undergo a ligand exchange process which has been investigated by NMR. A mechanism of this process is suggested.

Synthesis of N(CH2CH2CH2)(3)SnF . H2O (1a) and MeN(CH2CH2CH2)(2)SnFMe . H2O (5a) and molecular structures of 1a and N(CH2CH2CH2)(3)SnX (2, X = Cl; 3, X = Br; 4, X = I) are reported. Compound la is a tetramer held together by intermolecular Sn...F interactions (2.797(6) Angstrom) and F...H and O...H hydrogen bridges. It is the first example of an intermolecular hexacoordinated triorganotin halide. Compounds 2-4 exhibit the expected propellane (metallatrane) structure with pentaccordinate tin, with the shortest intramolecular Sn...N interaction of 2.28(2) Angstrom found for 3. The Sn...N distances in the other stannatranes are 2.393(5) and 2.426(6) (1a), 2.38(2) (2, hexagonal), 2.38(4) (2, monoclinic), and 2.375(6) Angstrom (4).

Determination of Small Quantities of Residue Phosphate in Tris-Sodium Phosphane Formiate by Means of 31P NMR Spectroscopy The concentration of residue phosphate in tris-sodium-phosphon-formiate (TPF·6H2O) water solutions has been determined via comparing integration of the 31P n.m.r. signal of the residue phosphate and one of the 31C NMR satellites of the TPF·6H2O 31P n.m.r. signal. The 31P n.m.r. spectra have been obtained in inverse gated detection mode; statistical methods of validation prove the certainty of the phosphate concentrations obtained to be excellent and strongly recommend the quantitative method employed for the detection of concentrations down to 0,1%.

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The chlorination of one (WP) bond of [(CO)4W(eta4-P4{W(CO)5}4)] is observed on reaction with PCl5 in CH3CN. The dichloro derivative [{(CH3CN)2(CO)2WCl}(eta3-p3{W(CO)5}2P{(Cl)W(CO)5})] is easily transformed into the more stable phosphahydroxy complex [{(CH3CN)2(CO)2WCl}(eta3-P3{W(CO)5)2P((OH)W(CO)5})]. The ''butterfly'' type P4-ring coordinates as a eta3-P4 ligand to a capping [(CH3CN)2(CO)2WCl] unit. Only three phosphorus atoms of the P4-ring are bonded to [W(CO)5] moieties.

The reaction of M(I)P(SiMe3)2 (M(I) = Li, Na, K) with diorganylchlorophosphines forms tris(diorganylphosphino)phosphines P(PR2)3 (R = Cy, Ph, i-Pr, n-Pr, Et, Me). In all cases, the stepwise formation reaction proceeds via di- and triphosphines resulting in iso-tetraphosphines which are stable in solution. Only the compounds with bulky substituents (R = Cy, Ph) can be isolated. By using quantumchemical procedures it is possible to get information about the pyramidal structure and the reaction behaviour. In agreement with these results orbitally controlled reactions occur where nucleophiles attack the central phosphorus atom.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis and 1H-NMR Spectroscopic Investigations of New Curcumin Analoga The synthesis of numerous symmetric and non-symmetric curcumin(hetero) analoga (1–3) systematic variation of the conjugated chain and substituents is described. The structure of most compounds is confirmed by 1H-n.m.r.-spectroscopy. All compounds show E-configuration. Conjugation and tautomerism are discussed based on spectroscopic data.

Journal für Praktische Chemie/Chemiker-ZeitungVolume 334, Issue 2 p. 181-182 Article Eine 2D-INEPT-Variante zur Detektierung wenig empfindlicher Kerne Detection of Less Sensitive Nuclei by Means of a Special 2D INEPT Version M. Dargatz, M. Dargatz Fachbereich Chemie der Martin-Luther-Universität Halle-Wittenberg Weinbergweg 16 O-4020 Halle/Saale, Bundesrepublik DeutschlandSearch for more papers by this authorProf. Dr. E. Kleinpeter, Corresponding Author Prof. Dr. E. Kleinpeter Fachbereich Chemie der Martin-Luther-Universität Halle-Wittenberg Weinbergweg 16 O-4020 Halle/Saale, Bundesrepublik DeutschlandFachbereich Chemie der Martin-Luther-Universität Halle-Wittenberg Weinbergweg 16 O-4020 Halle/Saale, Bundesrepublik DeutschlandSearch for more papers by this author M. Dargatz, M. Dargatz Fachbereich Chemie der Martin-Luther-Universität Halle-Wittenberg Weinbergweg 16 O-4020 Halle/Saale, Bundesrepublik DeutschlandSearch for more papers by this authorProf. Dr. E. Kleinpeter, Corresponding Author Prof. Dr. E. Kleinpeter Fachbereich Chemie der Martin-Luther-Universität Halle-Wittenberg Weinbergweg 16 O-4020 Halle/Saale, Bundesrepublik DeutschlandFachbereich Chemie der Martin-Luther-Universität Halle-Wittenberg Weinbergweg 16 O-4020 Halle/Saale, Bundesrepublik DeutschlandSearch for more papers by this author First published: 1992 https://doi.org/10.1002/prac.19923340216AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume334, Issue21992Pages 181-182 RelatedInformation

The reaction of white phosphorus with Fe2(CO)9 in refluxing benzene affords [{Fe(CO)4(mu-P2)}2{mu-Fe2(CO)6}2] (1). The structure of 1 was determined by X-ray crystallography; space group P2(1)/c, a 1718.3(6), b 1038.3(3). c 2016.8(5) pm, beta-115.87(2)-degrees at -95-degrees-C. The asymmetric unit consists of two half-molecules, the other halves of which are generated by crystallographic inversion. A rectangular P4 unit is bridged by [Fe(CO)4] groups on its shorter sides (d(PP) = 213.0(3), 212.4(4) pm) whereas the longer sides are bridged by [Fe2(CO)6] groups (d(PP) = 260.3(3), 260.3(4) pm). The four phosphorus atoms and the iron atoms of the [Fe(CO)4] groups form a plane, to which the [Fe2(CO)6] groups are orthogonal. In an uncommon bonding mode the P4 ligands provide 16 electrons for the cluster.

Na2[FePc].5.5THF (H2Pc = phthalocyanine; dmgH2 = dimethylglyoxime; Pr = n-propyl; Ph = phenyl; py = pyridine; THF = tetrahydrofuran) reacts with 1-bromalk-1-ynes PhC = CBr and PrC = CBr under oxidative addition to give the alkinyl iron(II)-phthalocyanin complexes Na[PcFeC = CPh].5THF (I) and Na[PcFeC = CPr].3THF (II), respectively. I reacts with pyridine to give Na[PcFeC = CPh].1.5py.2THF (III), which has also been prepared directly from FePc.2py and PhC = CNa.However, [Rh(PPh3)(dmgH)2]- reacts with PhC = CBr and PrC = CBr to give the vinyl rhodium(III) complexes Rh(PPh3)(dmgH)2(CH = CHPh) (IV) and Rh(PPh3)(dmgH)2(CH = CHPr) (V), respectively. IV and V are also obtained when [Rh(PPh3)(dmgH)2]- is reacted with the alkynes PhC = CH and PrC = CH.The constitution of I-V has been proved by elemental analysis, IR spectroscopy and in the case of IV and V by splitting off the organyl group protolytically with p-toluenesulfonic acid and reductively with LiAlH4. The C-13- and H-1-NMR spectra of IV and V show that they are vinyl complexes.

M(I)P(SiMe3)2(M(I) = Li, Na, K) reacts with diorganochlorophosphines to form iso-tetraphosphines of the type P(PR2)3 (R = Ph, Cy). The reaction follows a stepwise pathway via di- and tri-phosphines as shown by P-31-NMR. In the case of tBu2PCl the reaction stops on the step of the triphosphine (tBu2P)2PH. The reactivity of the alkali phosphides M(I)P(SiMe3)2 decreases in the sequence K > Na > Li.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Bis(trimethylsilyl)phosphides of alkali metals, MP[Si(CH3)3]2 (M = Li 3, Na 4, K 5, Rb 6, Cs 7), were prepared by reaction of bis(trimethylsilyl)phosphine with the appropriate alkali metal in the presence of naphthalene or with the metal hydride. The position of the P-31-NMR-signal is shifted to lower field with increasing ordering number of the alkali metal ion in the phosphide (delta: 3 almost-equal-to 4 < 5 < 6 < 7). 3 and 4 form solvates. A simpler preparation of P[Si(CH3)3]3 is described.

Abstract Treatment of [M(acac)2] (M=Ni, Pd, Pt) with the secondary phosphane sulfides R2P(S)H (R=Ph, But) affords the complexes [M2(μ-SPR2)2(η2-SPR2)2] whose structure markedly depends on the organic substituents at phosphorus. Thus, the phosphorus atoms around the metal atoms are mutually cis positioned for R=Ph and trans positioned for R=But, respectively. These metal(II) complexes (M=Pd; R=Ph) undergo redox reactions with the metal(O) complexes [M′(PPh3)2L](M′=Pd, Pt; L=2PPh3, C2H4) to produce homo- and heterodinuclear metal(I) complexes [PdM′(μ-SPPh2)2(PPh3)2] (M′=Pd, Pt). The structure of [Pd2(μ-SPBut2)2(η2-SPBut2)2] has been determined by single crystal X-ray diffraction. The complex crystallizes in the triclinic space group P 1 with a=10.315(3), b=10.668(3), c=11.181(3) A, α=72.95(2), β=75.20(2), γ=71.97(2)°, Z=1, Dexp=1.38(1), Dcalc=1.392 g cm−3. The structure was solved by heavy atom method and refined by full-matrix least-squares treatment to R=0.053 (Rw=0.052). The structure represents a centrosymmetric dinuclear complex with a six-membered (PdPS)2 core. The But2PS− ligands are coordinated in the bridging as well as in the dihapto mode.

AbstractThe title compound (III) (space group P1 with Z=2) is also characterized by 1H, 13C and 31P NMR spectroscopy.