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  • 1975-1979  (31)
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  • 1
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Behavior of Mono- and Diorganylphosphine Sulfides towards Metal Carbonyl Systems, IXReactions with the SH Group of Pentacarbonyl(mercaptodimethylphosphine)chromium(O)The acidic SH group in the complex (OC)5CrP(CH3)2SH (1) can be methylated with CH2N2 to give 2. The anion in 3a, b is obtained by reaction of N(C2H5)3 or sodium with 1. The binuclear via phosphorus and sulfur linked dichromate anion in 5 Results from 3a and (OC)5CrTHF. The i. r., 1H, and 31P n. m. r. spectra of the new prepared compounds 2, 3a, b, and 5 as well as a correlation between the 31P n. m. r. spectra and v(P-S) are discussed.
    Notes: Die acide SH-Gruppe im Komplex (OC)5CrP(CH3)2SH (1) läßt sich mit CH2N2 zu 2 methylieren. Das Anion in 3a, b erhält man durch Einwirkung von N(C2H5)3 oder Natrium auf 1. Aus 3a und (OC)5CrTHF entsteht das zweikernige, über Phosphor und Schwefel verbrückte Dichromat-Anion in 5. Die IR-, 1H- und 31P-NMR-Spektren der neu dargestellten Verbindungen 2, 3a, b and 5 sowie ein Zusammenhang zwischen den 31P-NMR-Spektren und v(P-S) werden diskutiert.
    Additional Material: 1 Ill.
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  • 2
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Directed Synthesis of Sulfinato-O and -S Complexes of Some Transition Metals, XVII. The Coordination Chemical Behaviour of the Silver Sulfinates RSO2Ag towards TriphenylphosphineThe remarkably stable complexes of the type (RSO2)Ag(PPh3)n (n = 1 (2), 2 (3), 3 (4) are obtained by the stepwise addition of triphenylphosphine to the silver sulfinates RSO2Ag (1). According to the i. r. spectra, the compounds 2 (coordination number (cn) = 2) and 4 (cn = 4) contain a sulfinato-O linkage, in the compounds 3 (cn = 4), however, a sulfinato-O,O′ linkage is present. The bonding of the RSO2- ligand via “hard” oxygen to the “soft” silver(I) ion is due to its weak π-donor ability.
    Notes: Durch schrittweise Addition von Triphenylphosphin an die Silbersulfinate RSO2Ag (1) werden die bemerkenswert stabilen Komplexe des Typs (RSO2)Ag(PPh3)n (n = 1 (2), 2 (3), 3 (4) erhalten. Den IR-Spektren zufolge liegt in den Verbindungen 2 (Koordinationszahl (KZ) = 2) und 4 (KZ = 4) eine Sulfinato-O-, in den Verbindungen 3 (KZ = 4) dagegen eine Sulfinato-O,O′-Verknüpfung vor. Die Bindung des RSO2--Liganden über den „harten“ Sauerstoff an das „weiche“ Silber(I)-Ion ist auf dessen geringe π-Donorfähigkeit zurückzuführen.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Behavior of Mono- and Diorganylphosphine Sulfides towards Metal Carbonyl Systems, XII. The Isomerization of Secondary Phosphine Oxides on Carbonyl(halogeno) Metal Complexes of Manganese and RheniumSecondary phosphine oxides R2HPO (R = C6H5 (2a), CH3 (2b)) can be transformed into the complex-stabilised phosphinic acids R2POH on the pentacarbonyl(halogeno)manganese and -rhenium systems XM(CO)5 (4, 5). In contrast to the extremely labile O-isomers (CO)4XReOPHR2 (3) the P-isomeric manganese and rhenium compounds (CO)4XMPR2OH (6, 7) are very stable. The IR, Raman, 1H, and 31P NMR spectra are discussed.
    Notes: Die sekundären Phosphinoxide R2HPO (R = C6H5 (2a), CH3 (2b)) lassen sich gemäß Gl. (2) an den Pentacarbonyl(halogeno)mangan- bzw. -rhenium-Systemen XM(CO)5 (4, 5) in die komplexstabilisierten phosphinigen Säuren R2POH überführen. Die P-isomeren Mangan- und Rhenium-Komplexe (CO)4XMPR2OH (6, 7) sind gegenüber den außerordentlich labilen O-Isomeren (CO)4XReOPHR2 (3) sehr beständig. Die IR-, Raman-, 1H- und 31P-NMR-Spektren werden diskutiert.
    Additional Material: 2 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 108 (1975), S. 291-300 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Directed Synthesis of Sulfinato-O and -S Complex of Transition Metals, XI. Linkage Isomerism in Sulfinato Complexes of Zinc(II)Starting from the sulfinato-O, O′ complexes (RSO2)2Zn(OH2)2(1a, b) the mono-, bis-, and tris(2, 2′-bipyridyl) complexes 2a, b, 3a, b, and 4a, b are produced according to equation (1) by stepwise addition of 2, 2′-bipyridyl. In the case of the bis(2, 2′-bipyridyl) complexes 3a, b the linkage-isomeric sulfinato-O and -S complexes 3aO, 3bO, and 3aS, 3bS are obtained. From 4a, b 1 mole of 2, 2′-bipyridyl can be eliminated reversibly with acetone according to equation (7) with formation of 3aO and 3aO. The newly prepared compounds were characterized on the basis of their i. r. spectra. In the case of 4a, b DTA, TG, and DTG measurements were carried out.
    Notes: Gemäß Gl. (1) gelingt, ausgehend von den Sulfinato-O, O′-Komplexen (RSO2)2zn(OH2)2 (1a, b), die schrittweise Addition von 2,2′-Bipyridyl, wobei die Mono-, Bis-und Tris(2,2′-bipyridyl)-Komplexe 2a, b, 3a, b und 4a, b entstehen. Im Falle der Bis(2,2′-bipyridyl)-Komplexe 3a, b wurden die bindungsisomeren Sulfinato-O-und-S-Komplexe 3aO, 3bO und 3aS, 3bs erhalten. Aus 4a, b läβt sich mit Aceton reversibel ein mol 2, 2′-Bipyridyl gemäß Gl. (7) unter Bildung von 3aO und 3bO abspalten /die neu dargestellten Verbindungen werden IR-spektroskopisch charakterisiert. Im Falle von 4a, b sind DTA-, TG- und DTG-Messungen durchgeführt worden.
    Additional Material: 1 Tab.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 110 (1977), S. 463-467 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Directed Synthesis of Sulfinato-O and -S Complexes of Some Transition Metals, XIV Sulfinato-O,S Complexes of Palladium(II) and Rhodium(III)The directed preparation of the sulfinato-O,S complexes {R(O)OS}nM (2a, b; 5a, b) was successful for the first time by elimination of coordinated water from the sulfinato-S complexes {RS(O)2}nM(OH2)n [n = 2, M = Pd (1a, b); n = 3, M = Rh (4a, b)] by 2,2-dimethoxypropane. The O,S-linkage is unequivocally shown from their chemical behaviour and the i. r. spectra. The criteria necessary for the formation of sulfinato-O,S complexes are discussed.
    Notes: Durch Abspaltung von koordiniertem Wasser aus den Sulfinato-S-Komplexen {RS(O)2}nM(OH2)n [n = 2, M = Pd (1a, b); n = 3, M = Rh (4a, b)] mit 2,2-Dimethoxypropan gelang erstmals die gezielte Darstellung der Sulfinato-O,S-Komplexe {R(O)OS}nM (2a, b; 5a, b). Die O,S-Verknüpfung ergibt sich eindeutig aus dem chemischen Verhalten und den IR-Spektren. Die für die Bildung von Sulfinato-O,S-Komplexen notwendigen Kriterien werden diskutiert.
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  • 6
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Behavior of Mono- and Diorganylphosphine Sulfides towards Metal Carbonyl Systems, XV: Reactions at the Functional SH Group of Complex-stabilized Dimethylthiophosphinous AcidThe thiophosphinous acid complex LnMnPR2SH (1) (LnMn = π-C5H5Mn(CO)2: R = CH3) is obtained from R2HPS and LnMnTHF 1 can be oxidized with oxygen to the disulfide[LnMnPR2S—]2 (2) The acidic character of the SH proton in 1 is proved with CH2N2, sodium, or N(C2H5)3 whereby the methyl ester 3 and the salts Kat[LnMnPR2S] (4a,b) are formed. Acylation of 4a leads to the acyl derivatives LnMnPR2SCOR (5a-c), which on warming eliminate CO with the formation of the alkyl compounds LnMnPR2SR (7b,c). The monosulfide [LnMnPR2]2S (6) is obtained from 4a and LnMnPR2Cl. The properties of the newly prepared compounds and their structures are discussed on the basis of IR, 1H and 31P NMR spectra.
    Notes: Den Thiophosphinig-Säure-Komplex LnMnPR2SH (1) (LnMn = π-C5H5Mn(CO)2: R = CH3) erhält man aus R2HPS und LnMnTHF. 1 läßt sich mit Sauerstoff zum Disulfid [LnMnPR2S—]2 (2) oxidieren. Der acide Charakter des SH-Protons in 1 wird durch Umsetzung mit CH2N2. Natrium oder N(C2H5)3 nachgewiesen, wobei der Methylester 3 und die Salze Kat[LnMnPR2S] (4a,b) entstehen. Acylierung von 4a führt zu den Acylderivaten LnMnPR2SCOR (5a-c), welche beim Erwärmen unter Bildung der Alkylverbindungen LnMnPR2SR (7b,c) CO abspalten. Das Monosulfid [LnMnPR2]2S (6) erhält man aus 4a und LnMnPR2Cl. Die Eigenschaften der neu dargestellten Verbindungen und ihre Konstitutionen werden mit Hilfe von IR-, 1H- und 31P- NMR-Spektren diskutiert.
    Additional Material: 3 Tab.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 773-775 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dimerization of Diphenyl(trifluoroacetyl)phosphane OxideAt -25°C the phosphane oxide CF3C[(O)P(O)Ph2]2OC(O)CF3 (1) dimerizes to the trifluoroacetate CF3C[(O) PPh2]2OC(O)CF3 (2a), which is sensitive to hydrolysis and, at 40°C is transformed irreversibly into the phosphinate CF3C[(O)PPh2][OP(O)Ph2]C(O)CF3(3a). In contrast to 2a, the thermally more stable homologous octanate C7F15C[(O)PPh2]2OC(O)C7F15 (2b) is obtained from Ph2PCI and C7F15CO2H.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 112 (1979), S. 763-772 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparation and Reactive Behaviour of Acyldiorganylphosphane OxidesThe acylphosphane oxides RC(O)P(O)R′R″ (3) are obtained in the case of 3a - e by oxidation of the acylphosphanes RC(O)PR′R″ (1a - e) with rigorously dried oxygen. 3c - e are also formed from the anhydrides (RCO)2O (R = CH3 CF3) and the phosphane oxides XP(O)R′R″ (2c′ d′). 3f only results from ClPPh2 and formic acid [eqs. (2a - c)]. 3d, e dimerize to the phosphinates RC[Ph2P(O)][OP(O)Ph2]C(O)R (4d, e)[eq.(3)] Heating of 3e with ClRh(PPh3)3 causes elimination of CO and formation of C2F6 and [Ph2P(O) — ]2 [eq. (4)]. Thermolysis of 3a - e generates the ketenes X2C2O (X = H, F) and the phosphane oxides 2a′ - e′ [eq. (5)], whereas 3f yields CO and 2d′ [eq. (6)]. 2c′ reacts with 3c to give the alcohol CH3C[(CH3)2P(O)]2OH (5c). With stoichiometric amounts of water 3a, b, d - f are hydrolyzed to the corresponding alcohols RC[R′R″P(O)]2 OH (5a, b, d - f), which isomerize with the exception of 5a to the phosphinates RC[R′R″P(O)][OP(O)R′R″]H (6b - f) [eqs. (7a, b)].
    Notes: Die Acylphosphanoxide RC(O)P(O)R′R″ (3) erhält man im Falle von 3a - e durch Oxidation der Acylphosphane RC(O)PR′R″ (1a - e) mit rigoros getrocknetem Sauerstoff. 3c - e bilden sich auch aus den Anhydriden (RCO)2O (R = CH3, CF3) und Phosphanoxiden XP(O)R′R″ (2c′, d′). 3f entsteht nur aus CIPPh2 und Ameisensäure [Gln. (2a - c)]:3d, e dimerisieren zu den Phosphinaten RC[Ph2P(O)][OP(O)Ph2]C(O)R (4d, e) [Gl. (3)]. Beim Erhitzen eliminiert 3e mit ClRh(PPh3)3 CO unter Bildung von C2F6 und [Ph2P(O)—]2 [Gl. (4)]. Während 3a - e bei der Thermolyse die Ketene X2C2O(X = H, F) und die Phosphanoxide 2a′-e′ liefern [Gl. (5)], gibt 3f CO und 2d′ [Gl. (6)]. 2c′ und 3c reagieren zum Alkohol CH3C[(CH3)2P(O)]2OH(5c). Mit stöchiometrischen Mengen Wasser hydrolysieren 3a, b, d - f zu den entsprechenden Alkoholen RC[R′R″(O)]2 OH (5a, b, d - f), welche sich mit Ausnahme von 5a in die Phosphinate RC[R′R″P(O)][OP(O)R′R″]H (6b - f) isomerisieren [Gln. (7a, b)].
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 3048-3057 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Preparative, Spectroscopic, and Structural Investigations on Organyl IVb-Element Seleninic Acid DerivativesThe seleninic acid derivatives R3EO2SeR′ [E = Pb (1), Sn (2), Ge (3), Si (4), C (5); R = CH3, C6H5:R′ = CH3 (a, d), C2H5 (b, e), C6H5 (c, f)] are obtained by reaction of triorganyl IVb-element halides R3EX (X = Cl, Br) with sodium or silver seleninates R′SeO2M. The lead and tin compounds 1 and 2 exist as polymeric seleninato-O, O′ complexes with the coordination number 5. While the germanium and silicium derivatives 3 and 4 are esters, in which the Ge and Si atoms are linked by only one O-atom to the R′SeO2- ligands, (C6H5)3CSe(O)2C6H5 (5f) is a selenone. The IR, Raman, 1H, 77Se, 13C NMR, and Mößbauer spectra are discussed. (CH3)3SnO2SeCH3 (2a) crystallizes in the monoclinic system, space group P21/c with Z = 8.
    Notes: Durch Umsetzung verschiedener Triorganyl-IVb-Elementhalogenide R3EX (X = Cl, Br) mit Natrium- oder Silberseleninaten R′SeO2M erhält man die Seleninsäurederivate R3EO2SeR′ [E = Pb (1), Sn (2), Ge (3), Si (4), C (5); R = CH3, C6H5: R′ = CH3 (a, d), C2H5 (b, e), C6H5 (c, f)]. Die Blei- und Zinnverbindungen 1 und 2 liegen als polymere Seleninato-O, O′-Komplexe mit der Koordinationszahl 5 vor. Während es sich bei den Germanium- und Silicium-Derivaten 3 und 4 um Ester handelt, in denen die Ge- und Si-Atome über nur ein O-Atom an die R′SeO2-Liganden gebunden sind, ist (C6H5)3CSe(O)2C6H5 (5f) ein Selenon. Die IR-, Raman-, 1H-. 77Se-, 13C-NMR- und Mößbauer-Spektren werden diskutiert. (CH3)3SnO2SeCH3 (2a) kristallisiert monoklin in der Raumgruppe P21/c mit Z = 8.
    Additional Material: 1 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 111 (1978), S. 2455-2457 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Selenium Dioxide Insertion into Tin-Oxygen BondsThe monomeric selenites [R3SnO]2SeO (1) [R = CH3 (a), n-C4H9 (b), C6H5 (c)] are obtained by insertion of SeO2 into the Sn—O bonds of bis(triorganyltin) oxides [R3Sn]2O. 1c is also formed from [(C6H5)3Sn]2E (E = S, Se) and SeO2. Depending on the stoichiometric ratio the reaction of (CH3)3SnOH with SeO2 yields 1a or (CH3)3SnOSe(O)OH (2a).
    Additional Material: 1 Tab.
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