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1.
Metal Complexes of Phosphinic Acids. XVIII. Ansa- and Oligo-Complexes of Bifunctional Dithiophosphinic Acids The influence of R′ in the bifunctionell chelate ligands ?S(S)P(R)? R′? (R)P(S)S? on the association of their planar NiII and tetrahedral CoII complexes is investigated by vapour pressure osmometry and in the case of diamagnetic NiII compounds also by 31P-NMR spectroscopy. While insoluble coordination polymers [S2P(R)? R′? (R)PS2M]x (M = NiII, CoII) are formed with R′ = p-(C2H4)2C6H4 it can be shown, that in solutions of the complexes with R′ = o-(C2H4)2C6H4 and R′ = o-(C3H6)2C6H4 there exists an association equilibrium comprehending oligomers with n ? x. Above all in the latter case steric conditions seem to favour intramolecular chelating and thus formation of ansa-type complexes. Synthesis of the ligands and the complexes is described. 相似文献
2.
Ulrich Wannagat Rainer Münstedt 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2-4):233-237
Abstract Dialkylbenzylphosphine imides C6H5CH2–PRR′[dbnd]N″ (R, R′ = CH3, C2H5; R″ = H, CH3, Si(CH3)3 react with aliphatic and aromatic aldehydes in benzene solution on heating to 80°C directly and in high yields according to a Horner-Wittig-reaction with formation of an olefine whereas ketones like benzophenone and acetophenone only perform an O/NR″ exchange (R″ = H). Dialkylbenzylphosphinimide C6H5CH2–PRR′[dbnd]N″ mit R, R′ = CH3, C2H5 und R″ = H, CH3, Si(CH3)3 reagieren mit aliphatischen und aromatischen Aldehyden in benzolischer Lösung beim Erwärmen auf 80°C direkt und mit hohen Ausbeuten im Sinne einer Horner-Wittig-Reaktion unter Olefinbildung, während sich mit Ketonen wie Benzophenon oder Acetophenon nur ein O/NR″-Austausch (R″ = H) vollzieht. 相似文献
3.
Yurii S. Nekrasov Svetlana Yu. Sil'vestrova Aleksandr I. Grigo'ev Lyudmila N. Reshetova Viktor A. Sipachev 《Journal of mass spectrometry : JMS》1978,13(9):491-494
The electron impact mass spectra of eight polynuclear beryllium complexes Be4O(RCO2)6 (R?H, CH3, C2H5) and Be4O(RCO2)5OR′ (R?CH3, R′?H, CH3, C2H5, C3H7; R?C2H5, R′?C2H5) are reported. The major fragmentations involve the elimination of (RCO)2O (RCOOR′) or Be(RCO2)2 (Be(RCO2)OR′) from the ions [M? L]+ and of {(R? H)CO}, (R′? H), H2O and BeO from the lighter ions. The fragmentation patterns are practically independent of the organic groups present and can be rationalized by stereochemical considerations. 相似文献
4.
Preparation of New Alkylaminofluorosilanes Aminofluorosilanes of the composition RSiF2NR′R″ (R = H, CH3, C2H3, C6H5; R′ = Si(CH3)3; R″ = C(CH3)3; R′ = R″ = i-C3H7), as well as C6H5SiF2N[C(CH3)2CH2]2CH2 are obtained by the reaction of fluorosilanes with the lithium salts of the corresponding amines in a molar ratio 1:1. The further reaction of these compounds with the lithium salts of alkylamines and anilin leads to the formation of the diaminofluorosilanes RSiFNR′R″NHR? (R? = C(CH3)3, i-C3H7, C6H5). The 1H, 19F, 29Si n.m.r. and mass spectra of the above mentioned compounds are reported. 相似文献
5.
Compounds of the composition RR′SiFNR″Si(CH3)3 (R = H, F, CH3, C2H5, C3H7, C2H3, C6H5, C(CH3)3; R = F, CH3, C6H5; R″ = CH3, C(CH3)3, Si(CH3)3) are obtained by the reaction of silicontetrafluoride or organo-substituted silicon-fluorides with the lithium salts of alkylsilylamines in a molar ratio of . The disubstituted compounds RSiF(NR′Si(CH3)3)2 (R = H, F, CH3, C2H3, C6H5; R′ = CH3, C(CH3)3) result when the reactants are in a molar-ratio. Likewise the unsymmetrical siliconfluorsilylamines of the formulae F2Si(NRSi(CH3)3) (NR′Si(CH3)3) (R = CH3, R′ = C(CH3)3), as well as the trisubstituted compounds FSi(NCH3Si(CH3)3)3 and FSi(NCH3Si(CH3)3)2(N(Si(CH3)3)2) were made. By reacting phenyltrifluorsilane with dialkylamines () C6H5SiF2NR2(R = CH3, C2H5) was obtained. The IR-, mass-, 1H and 19F NMR spectra of the above-mentioned compounds are reported. 相似文献
6.
On Chalcogenolates. 81. Studies on N-Hydroxy Dithiocarbamic Acid. 3- Esters of N-Hydroxy Dithiocarbimic Acid and Dithiocarbamic Acid The reaction between hydroxylamine, carbon disulfide, and alkyl halide leads to the corresponding ester of N-hydroxy dithiocarbimic acid HO? N?C(SR)2 with R = CH3, C2H5; R2 = ? CH2? CH2? . The phenyl ester of N-hydroxy dithiocarbamic acid HO? NH? CS(SC6H5) has been prepared by reaction of hydroxylammonium chloride with the phenyl ester of chlorodithioformic acid. N-Methyl hydroxylammonium chloride reacts with carbon disulfide and alkyl iodide to form the corresponding ester of the dithiocarbamic acid HO? N(CH3)? CS(SR) with R = CH3, C2H5. The unstable compounds have been characterized by different methods. 相似文献
7.
Bis(trimethylsilyl)hypophosphite und Alkoxycarbonylphosphonous Acid Bis(trimethylsilyl) esters as Building Blocks in Organophosphorus Chemistry The oxidation of pure bis(trimethylsilyl)hypophosphite ( BTH ) with chalcogenides forming (Me3SiO)2P(X)H (X = O, S, Se, Te) is described as well as its reactions with alkylhalides RX (X = Cl, Br, I) and Cl? C(O)OR (R = Me, Et, Bzl). By reaction with oxygen, sulfur, and selenium the alkoxycarbonylphosphonous acid bis(trimethylsilyl)esters form RO? C(O)? P(X)(OSiMe3)2 (X = O, S, Se) whereas with Cl? C(O)OR the bis(alkoxycarbonyl)-phosphinic acid trimethylsilylesters are obtained. After partial hydrolysis the resulting instable RO? C(O)? P(O)H(OSiMe3) gives RO? C(O)? P(O)(OSiMe3)? CH2? NH? A? COOR′ (A = CH2, CH2CH2, CHCH3, CH2CH2SH, CHCH(CH3)2,…) when allowed to react with hexahydro-s-triazines of the aminoacid esters. Reactions of the alkoxycarbonyl-P-silylesters with NaOR or NaOH result in the corresponding mono-, di-, or trisodium salts. With mineral acids decarboxylation occurs, but H? P(O)(OH)? CH2? NH? A? COOH can be obtained, too. The structure of the compounds described are discussed by their n.m.r. data. 相似文献
8.
Transition Metal Complexes [Et2P(S)NR]M/n, Chelates containing 4-membered Rings and Phosphinothioic-organylamidato Ligands Phosphinothioic-organylamidato complexes [Et2P(S)NR]M/n (R = Me, Et, tBu, cHex, Ph; M = TiIII, VIII, CrIII, CoII, ZnII) are obtained by reaction of metal halides with [Et2P(S)NR]Li or from ZnEt2 and Et2P(S)NHR. In contrast to the analogous phosphinothioic complexes [R′2P(S)X]M/n (X = O, S, Se) they are extremely hydrolyzable. The ligand field parameters Δ and β of Et2P(S)NR? are found to be similar to those of R′2P(S)S? indicating a low ligand field strength and a strong nephelauxetic effect. In contrast to [R′2P(S)O]2M (M = Co, Zn), which are highly polymerised, there is only a weak tendency of the corresponding tetrahedral phosphinothioicorganylamidato complexes to form ligand bridges. 相似文献
9.
Ludwig Maier 《Helvetica chimica acta》1969,52(3):845-857
Bis-chloromethyl-alkyl-and - aryl-phosphine oxides, (CICH2)2P(O)R, which are obtained by reaction of (CICH2)2P(O)Cl with GRIGNARD reagents, undergo a MICHAELIS -ARBUSOV reaction when heated for several hours with trivalent phosphorus esters (phosphites, phosphonites, or phosphinites) at 170–180°C. The reaction affords bis-(dialkyloxyphosphonyl-methyl)-, bis (alkyloxyphosphinyl-methyl)-, and bis-(oxophosphoranyl-methyl)-, -alkyl- or -aryl-phosphine oxides, R(O)P[CH2P(O)R′R″]2 R = CH3, C2H5, n-C8H17, n-C12H25, C6H5; R′ and R″ = C2H5O, C4H9O, C6H5, CH3 in good yields. Conversion of the compounds containing alkyloxy groups to the free acids is achieved by refluxing with conc. HCl. Bis-(dihydroxyphosphonyl-methyl)-dodecylphosphine oxide, n-C12H25(O)P[CH2P(O) (OH)2]2, obtained by hydrolysis of the all-ethyl ester, titrates in aqueous solution as a tetrabasic acid with breaks at pH = 4 (two equivalents), pH = 6,9 (one equivalent) and pH = 9,6 (one equivalent). This acid, its disodium salt (m. p. 405–410°) and its tetrasodium salt (m.p. > 460°) are surface active and are excellent chelating agents. The 1H- and 31P-NMR. spectra of all the compounds prepared are discussed. 相似文献
10.
Coordination and Reactivity of Sulfinylimides RNSO in Cyclopentadienyldicarbonylmanganese Complexes The coordination behaviour of sulfinylimides RNSO (R = SiMe3, Ph) towards CpMn(CO)3 (Cp = C5H5, C5H4CH3) has been studied. Under total exclusion of water the substitution products CpMn(CO)2{S(O)NR} ( 2 a , b , 2 ′ a , b ) with μ1‐S‐linkage are formed. In the presence of water, however, the SO2 complexes 3 , 3 ′ as iminofree hydrolysis products are obtained. There are only spectroscopic indications for the directed hydrolytic conversion of the silyl derivatives 2 a , 2 ′ a into the unstable HNSO complexes 4 , 4 ′ by cleavage of the Si–N‐bond and retention of the cumulene moiety. The molecular structures of π‐C5H5Mn(CO)2{S(O)NSiMe3} ( 2 a ) and π‐C5H4CH3Mn(CO)2SO2 ( 3 ′) were elucidated by single crystal X‐ray analyses. 相似文献
11.
Birgit Dyckhoff Heinz-Josef Schulte Ulli Englert Thomas Paul Spaniol Wolfgang Klui Pius August Schubiger 《无机化学与普通化学杂志》1992,614(8):131-141
Rhenium Complexes Stabilized by Tris-chelating Oxygen Ligands: Potential New Radiopharmaca? Ris-chelating oxygen ligands of the general formula L? = [(C5H4R)Co{P(O)R′R″}3]? (R = COOCH3, COOH and R′ = OCH3; R = H and R′ = O(CH2)5COOCH3, O(CH2)5COOH; R″ = OCH3) have been synthesized. These ligands L? and others of the same type have been used to prepare the rhenium oxo complexes [LReO3] and [LReOX2] (X = Cl, Br, I). In order to judge their use in radioimmunotherapy the corresponding complexes containing radioactive rhenium isotopes have also been synthesized. The rhenium(VII) as well as the diamagnetic rhenium(V) complexes are stable in air in the solid state as well as in organic solvents. They hydrolyze slowly in water to yield perrhenic acid. The X-ray structures of the sodium salt Na[(C5H4COOCH3)Co{P(O)(OCH3)2}3] and of the rhenium complex [LReOBr2] (R = H, R′ = R″ = OCH3) have been determined. The sodium salt crystallizes in trimeric units with the composition [(NaL)3 · 3 H2O]. Each sodium has a distorted octahedral oxygen coordination. In [LReOBr2] the ReO4Br2 octahedron is only slightly distorted. 相似文献
12.
On Chalcogenolates. 140. Studies on Dialkyl Esters of Chalcogenocarbonic Acids. 3. S,Se-Dialkyl Dithiomonoselenocarbonates. Evidence for the Existence of Alkyl Selenoxanthates [S2C? SeR]? The esters RSe? CS? SR′ with R = R′ = C2H5, nC3H7 as well as with R = nC3H7 and R′ = C2H5 have been produced by three different methods. The compounds have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (1H, 13C, and 77Se), and mass spectra. The unstable alkyl selenoxanthates M[S2C? SeR], where M = Na, K and R = C2H5, nC3H7, are formed by reaction of carbon disulfide with the corresponding alkane selenolate. Freshly prepared they react with alkyl iodides R′I to yield RSe? CS? SR′. 相似文献
13.
On chalcogenolates. 138. Studies on Dialkyl Esters of Chalcogenocarbonic A cids. 1. O, Se-Dialkyl Monoselenocarbonates The esters RSe? CO? OR′ with R = R′ = C2H5 as well as with R = nC3H7 and R′ = CH3, C2H5 have been prepared by reaction of sodium alkane selenolates with alkyl esters of chloroformic acid. The compounds have been characterized by means of electron absorption, infrared, nuclear magnetic resonance (1H, 13C, and 77Se), and mass spectra. 相似文献
14.
Esters of the trimeric dithioformic acid [HCS(SR)]3 were prepared by interaction of K[HCS2] with alkyl iodides (R = CH3, C2H5). Orthoesters HC(SR)3 and di-orthoesters of the monomeric dithioformic acid were formed by reaction of formic acid with thioles (RSH mit R = CH3, C2H5, CH2C6H5) or dithioles (HS? (CH2)n? SH with n = 2, 3,4). The prepared compound were characterised by different methods. 相似文献
15.
α ω-Alkane-bis-dimethylarsine Sulfides and Selenides, a Novel Class of Ligands The reaction of α,ω-alkane-bis-dimethylarsanes (CH3)2As? (CH2)n? As (CH3)2 with sulfur and selenium results in formation of the sulfides and selenides, respectively, (CH3)2As(X)? (CH2)n? As(CH3)2 or (CH3)2As(X)? (CH2)n? As(X)(CH3)2 (X = S, Se), which form chelat-complexes with the salts CoX2 · 6 H2O (X = Cl?, Br?, I?, NO3?). The UV-spectra of the complexes are presented and discussed. 相似文献
16.
José Vicente Prof. Dr. José‐Antonio Abad Dr. María‐José López‐Sáez Dr. Peter G. Jones Prof. Dr. Delia Bautista Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(2):661-676
Complexes [Pd(C6H3XH‐2‐R′‐5)Y(N^N)] (X=O, NH; Y=Br, I; R′=H, NO2; N^N=N,N,N′,N′‐tetramethylethylenediamine (tmeda), 2,2′‐bipyridine (bpy), 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine (dtbbpy)) react with RN?C?E (E=NR, S) or RC≡N (R=alkyl, aryl, NR′′2) and TlOTf (OTf=CF3SO3) to give, respectively, 1) products of the insertion of the C?E group into the C? Pd bond, protonation of the N atom, and coordination of X to Pd, [Pd{κ2‐X,E‐(XC6H3{EC(NHR)}‐2‐R′‐4)}(N^N)]OTf or [Pd(κ2‐X,N‐{ZC6H3(NH?CR)‐2‐R′‐4})(N^N)]OTf, or products of the coordination of carbodiimides and OH addition, [Pd{κ2‐C,N‐(C6H4{OC(NR)}NHR‐2)}(bpy)]OTf; or 2) products of the insertion of the C≡N group to Pd and N‐protonation, [Pd(κ2‐X,N‐{XC6H3(NH?CR)‐2‐R′‐4})(N^N)]OTf. 相似文献
17.
Monomeric Dialkyl Metal Complexes of the R2M(NR′)2XR Type with M = Al, Ga, In, Tl; X = S, C and R, R′ = Alkyl and Silyl N,N′-Bis(trimethylsilyl)sulfurdiimide reacts with the trimethyl derivatives of aluminium, gallium, and indium within insertion. Hereby monomeric sulfinic acid imidamidates Me2M(NSiMe3)2SMe (Me = CH3) are formed. The lithium amidinates Li(NR′)2CMe (R′ = i-C3H7 and SiMe3) are formed likewise by insertion reactions with LiMe and the corresponding carbodiimides R′N?C?NR′ and were used in reactions with R2MCl (M = Al to Tl) to synthesize dialkyl metal amidinates R2M(NR′)2CMe. The NMR (1H and 13C) and the vibrational spectra (IR and Raman) are discussed and applied to describe the structure of these chelat complexes. 相似文献
18.
On Organophosphorus Compounds. XV. Preparation and Reactions of Trimethylsilyl Esters of Phosphinic Acids Trimethylsilylesters of Phosphinic acids R2P(X)YSi(CH3)3 (R ? CH3, C2H5, C3H7, t?C4H9, C6H5; X, Y ? O, S) were prepared by 7 different methods as in some cases easily hydrolysable but thermally remarkably stable compounds. The properties and some reactions of these substances are reported, their structures confirmed by IR? as well as 1H- and 31P-NMR-spectroscopy. Dimethylsilylen-bis(phosphinic acid esters) were obtained according to \documentclass{article}\pagestyle{empty}\begin{document}$ 2{\rm R}_{2} {\rm P(\rm X)\rm ONH}_{4} + {\rm R}_{\rm 2} {\rm SiCl}_{2} \to 2{\rm E NH}_{4} {\rm Cl + R}_{2} {\rm P(X) - O - SiR}_{2} - {\rm O - P(X)R}_{2} ({\rm R = CH}_{3};{\rm X = O,S}) $\end{document}. 相似文献
19.
Ludwig Maier 《Helvetica chimica acta》1969,52(3):858-871
Tris-chloromethyl-phosphine oxide, (ClCH2)3 P?O(I), is obtained by chlorination of (HOCH2)3P?O with PCl5 or (C6H5)3PCl2, and also by oxidation of (CICH2)3P?O and (ClCh2)2(CH3)P?O. High yields of tris-(dialkyloxyphosphonly-methyl)-phosphine oxides, [RO2(O)PCH2]2P?O (II) (R?CH3, C2H5, iso-C3H7, n-C4H9, 2- ethyl-hexyl), tris (alkyloxyphosphinyl-methyl)-phosphine oxides, [R2(O)PCH2]3P?O(R = C6H5, CH3) are obtained by heating tris-chloromethyl-phosphine oxides, [(RO) (R′) (O)PCH2]3P?O (R = C4H9, R′? C6H5) and tris-(oxophosphoranyl-phosphine oxides with phosphites, phosphonites and phosphinites, respectively, at 170–180°C for several hours. Compounds II possess an extraordinarily high absorption capacity. Thus a warm. 2% solution of II (R = C2H5) in benzene solidifies completely on cooling so that no benzene can be poured off. Tris-dihydroxyphosphonyl-methyl)-phosphine oxide, [(HO)2(O)PCH2]3P?O, obtained by hydrolysis of II (R ? C2H5) with refluxing conc. HCl or by thermal decomposition of II (R ? iso-C3H7) at 190°, titrates in aqueous solution as a hexabasic acid with breaks at pH = 4,4 (three equivalents) and pH = 10,7 (three equivalents). It forms crystalline salts with amines, alkali and alkaline earth metals, and is an excellent chelating agent. The 1H- and 31?P-NMR. spectra of all the compounds prepared are discussed. 相似文献
20.
Synthesis and Structural Studies of Aluminum Dialkylamines and Dialkylamides: N‐Chirality of (CH3)3AlNHRR′ and cis‐trans ‐Isomerism at X2AlNRR′ (X = CH3, Cl, H) Aluminum dialkylamines and dialkylamides were prepared from Al(CH3)3 and NH(CH3)R′ (R′: –C2H5, –tC4H9) and characterized by elemental analyses, 1H‐, 13C‐, and 27Al‐NMR spectroscopy. The crystal structures of [(CH3)2AlN(CH3)(–tC4H9)]2 ( IV ), [Cl2AlN(CH3)(C2H5)]2 ( V ), and [H2AlN(CH3)(C2H5)]∞ ( VI‐trans and VI‐cis ) are discussed. 相似文献