共查询到20条相似文献,搜索用时 31 毫秒
1.
Elise Duhamel Alpar Pöllnitz Adina Stegarescu Prof. Dr. Anca Silvestru 《无机化学与普通化学杂志》2011,637(10):1355-1360
Redistribution reactions between diorganodiselenides of type [2‐(R2NCH2)C6H4]2Se2 [R = Et, iPr] and bis(diorganophosphinothioyl disulfanes of type [R′2P(S)S]2 (R = Ph, OiPr) resulted in the hypervalent [2‐(R2NCH2)C6H4]SeSP(S)R′2 [R = Et, R′ = Ph ( 1 ), OiPr ( 2 ); R = iPr, R′ = Ph ( 3 ), OiPr ( 4 )] species. All new compounds were characterized by solution multinuclear NMR spectroscopy (1H, 13C, 31P, 77Se) and the solid compounds 1 , 3 , and 4 also by FT‐IR spectroscopy. The crystal and molecular structures of 3 and 4 were determined by single‐crystal X‐ray diffraction. In both compounds the N(1) atom is intramolecularly coordinated to the selenium atom, resulting in T‐shaped coordination arrangements of type (C,N)SeS. The dithio organophosphorus ligands act monodentate in both complexes, which can be described as essentially monomeric species. Weak intermolecular S ··· H contacts could be considered in the crystal of 3 , thus resulting in polymeric zig‐zag chains of R and S isomers, respectively. 相似文献
2.
[2-(Me2NCH2)C6H4]HgCl (1) was prepared by reacting HgCl2 with [2-(Me2NCH2)C6H4]Li in diethyl ether. The reactions of 1 with the sodium or ammonium salt of the appropriate thiophosphinato ligand, in 1:1 molar ratio, afford the isolation of [2-(Me2NCH2)C6H4]Hg[S(S)PR2] [R=Me (2), Et (3), Ph (4)], [2-(Me2NCH2)C6H4]Hg[S(O)PPh2] (5) and [2-(Me2NCH2)C6H4]Hg[S(S)P(OiPr)2] (6). The compounds were investigated by IR and multinuclear NMR (1H, 13C and 31P) spectroscopy. The molecular structures of 1 and 4 were determined by single-crystal X-ray diffraction. Due to the strong intramolecular coordination of the N atom of the pendant CH2NMe2 arm [Hg(1)-N(1) 2.764(6) and 2.725(4) Å in 1 and 4, respectively] both compounds exhibit a T-shaped (C,N)HgX core in the molecular unit, with almost linear arrangement of the covalent bonds [C(1)-Hg(1)-Cl(1) 176.93(18)° in 1, and C(1)-Hg(1)-S(1) 169.54(16)° in 4]. The crystals of 1 contain discrete monomeric molecules, while the crystals of 4 contain dimer associations built through asymmetric bridging dithiophosphinato ligands [Hg(1)-S(1) 2.3911(16) Å, Hg(1)?S(2a) 3.102(2) Å], thus resulting in an overall pseudo-trigonal bipyramidal (or seesaw) (C,N)HgS2 core, with the nitrogen atom and the weekly bonded sulfur atom in equatorial positions [N(1)-Hg(1)?S(2a) 82.01(10)°]. 相似文献
3.
Tomáš Řezníček Libor Dostál Aleš Růžička Jiří Kulhánek Filip Bureš Roman Jambor 《应用有机金属化学》2011,25(3):173-179
The phosphines L1PPh2 (1) and L2PPh2 (2) containing different Y,C,Y‐chelating ligands, L1 = 2,6‐(tBuOCH2)2C6H3? and L2 = 2,6‐(Me2NCH2)2C6H3?, were treated with PdCl2 and di‐µ‐chloro‐bis[2‐[(N,N‐dimethylamino)methyl]phenyl‐C,N]‐dipalladium(II) and yielded complexes trans‐{[2,6‐(tBuOCH2)2C6H3]PPh2}2PdCl2 (3), {[2,6‐(Me2NCH2)2C6H3]PPh2} PdCl2 (4), {[2,6‐(tBuOCH2)2C6H3]PPh2}Pd(Cl)[2‐(Me2NCH2)C6H4] (5) and {[2,6‐(Me2NCH2)2C6H3]PPh2}Pd(Cl)[2‐(Me2NCH2)C6H4] (6) as the result of different ability of starting phosphines 1 and 2 to complex PdCl2. Compounds 3–6 were characterized by 1H, 13C, 31P NMR spectroscopy and ESI‐MS. The molecular structures of 3,4 and 6 were also determined by X‐ray diffraction analysis. The catalytic activity of complexes 3–6 was evaluated in the Suzuki‐Miyaura cross‐coupling reaction. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
4.
Adina Rotar Markus Schürmann Richard A. Varga Cristian Silvestru Klaus Jurkschat Prof. Dr. 《无机化学与普通化学杂志》2008,634(9):1533-1536
Single‐crystal X‐ray diffraction analysis of [2,6‐(Me2NCH2)2C6H3]2SnF2 reveals that only one of the two dimethylaminomethyl groups of each pincer‐type ligands [2,6‐(CH2NMe2)2C6H3]? is coordinated to the tin atom at Sn‐N distances of 2.576(2) and 2.470(2) Å, inducing chirality of the latter. The tin atom exhibits a distorted octahedral trans(C,C)cis(N,N)cis(F,F) configuration. Extensive intra‐ and intermolecular C‐H···F hydrogen bonding is observed with the latter giving rise to formation of polymeric chains. 相似文献
5.
Răzvan Şuteu Ciprian I. Raţ Cristian Silvestru Andrada Simion Natalia Candu Vasile I. Pârvulescu Anca Silvestru 《应用有机金属化学》2020,34(4):e5393
The compounds [2-(Me2NCH2)C6H4]2SbL (L = ONO2 ( 2 ), OSO2CF3 ( 3 )) and [PhCH2N(CH2C6H4)2]SbL (L = ONO2 ( 5 ), OSO2CF3 ( 6 )) were prepared by reacting [2-(Me2NCH2)C6H4]2SbCl ( 1 ) and [PhCH2N(CH2C6H4)2]SbCl ( 4 ), respectively, with the appropriate silver(I) salt in a 1:1 molar ratio. The new species 2 – 6 were structurally characterized in solution using multinuclear NMR and in the solid state using infrared spectroscopy. The solid-state structures for compounds 2 , 4 and 6, as well as for the hydrolysis ionic product [{2-(Me2N+HCH2)C6H4}{2-(Me2NCH2)C6H4}SbOH][CF3SO3]− ( 3h ) were determined using single-crystal X-ray diffraction. Medium to strong intramolecular N→ Sb interactions were observed in all these four compounds, thus resulting in hypercoordinated organoantimony(III) species 14-Sb-6 in 2 and 10-Sb-4 in the cation of 3h and in 4 and 6 . Compounds 1 – 6 and the starting amines PhCH2NMe2 and PhCH2N(CH2C6H4Br-2)2 were investigated as catalysts in the Henry (nitroaldol) addition of nitromethane to benzaldehyde. The activity of compounds 1 – 6 resulted as an effect of the cooperation of the positively charged antimony with the negatively charged nitrogen. 相似文献
6.
Monika Kulcsar Cristian Silvestru John E. Drake Michael E. Hursthouse 《Journal of organometallic chemistry》2005,690(13):3217-3228
The cleavage of the Se-Se bond in [2-(Me2NCH2)C6H4]2Se2 (1) was achieved by treatment with SO2Cl2 (1:1 molar ratio) or elemental halogens to yield [2-(Me2NCH2)C6H4]SeX [X = Cl (2), Br (3), I (4)]. Oxidation of 1 with SO2Cl2 (1:3 molar ratio) gave [2-(Me2NCH2)C6H4]SeCl3 (5). [2-(Me2NCH2)C6H4]SeS(S)CNR2 [R = Me (6), Et (7)] were prepared by reacting [2-(Me2NCH2)C6H4]SeBr with Na[S2CNR2] · nH2O (R = Me, n = 2; R = Et, n = 3). The reaction of 3 with K[(SPMe2)(SPPh2)N] resulted in isolation of [2-(Me2NCH2)C6H4]Se-S-PMe2N-PPh2S (8). The compounds were characterized by solution NMR spectroscopy (1H, 13C, 31P, 77Se, 2D experiments). The solid-state molecular structures of 2, 4-8 were established by single crystal X-ray diffraction. All compounds are monomeric, with the N atom of the pendant CH2NMe2 arm involved in a three-center-four-electron N?Se-X (X = halogen, S) bond. This results in a T-shaped coordination geometry for the Se(II) atom in 2, 4, 6-8. In 5, the Se(IV) atom achieves a square pyramidal coordination in the mononuclear unit. Loosely connected dimers are formed through intermolecular Se?Cl interactions (3.40 Å); the overall coordination geometry being distorted octahedral. In all compounds hydrogen bonds involving halide or sulfur atoms generate supramolecular associations in crystals. 相似文献
7.
Adina Rotar Richard A. Varga Cristian Silvestru 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(8):m355-m356
The title compound, [Sn2(C9H12N)4O(OH)2], consists of two [2‐(Me2NCH2)C6H4]2SnOH units bridged by an O atom located on a twofold rotation axis. The unique Sn atom is six‐coordinated with a (C,N)2SnO2 octahedral core, as a result of the strong intramolecular N→Sn dative coordination trans to the Sn—O bonds [N—Sn—O = 170.24 (12) and 167.83 (10)°]. Owing to the presence of intermolecular H...phenyl contacts, the molecules are arranged in a ladder‐like structure. 相似文献
8.
Anton Hammerl Thomas M. Klapötke Prof. Dr. Burkhard Krumm Matthias Scherr 《无机化学与普通化学杂志》2007,633(10):1618-1626
The tellurenyl fluoride, 2‐Me2NCH2C6H4TeF, was obtained from reaction of the tellurenyl iodide RTeI with AgF. The compound was unambiguously identified by 19F and 125Te NMR spectroscopy. The decomposition under disproportionation leads to the tellurium(IV) trifluoride, 2‐Me2NCH2C6H4TeF3 and the ditelluride RTeTeR. The fluorination of the ditelluride, (2‐Me2NCH2C6H4Te)2, with XeF2 results in pure RTeF3. The molecular structure of 2‐Me2NCH2C6H4TeF3, the second structural characterized tellurium(IV) trifluoride, has been determined. Furthermore the syntheses of the new tellurium(IV) difluoride, (2‐Me2NCH2C6H4)2TeF2, and corresponding tellurium(IV) diazide, (2‐Me2NCH2C6H4)2Te(N3)2 as well as the tellurium(IV) triazide, 2‐Me2NCH2C6H4Te(N3)3, and their characterization by spectroscopic methods were reported. During these investigations a rather interesting tellurium(VI) species was formed and the molecular structure of a subsequent product, [(2‐Me2NHCH2C6H4)2TeF3O]2(SiF6), was elucidated. Theoretical investigations for the compounds containing the stabilizing 2‐dimethylaminomethylphenyl substituent are illustrated. 相似文献
9.
Treatment of the biphenyl derivative [S=C{(NCH2But)2C6H3‐3,4}]2 or [Cl2Si{(NCH2But)2C6H3‐3,4}]2 with C8K afforded the new bis(carbene) 1 or the first bis(silylene) 2 , respectively. The X‐ray structure of 2 is presented. 相似文献
10.
Xin‐Qiang Wang Wen‐Tao Yu Dong Xu Jian‐Dong Fan Guang‐Hui Zhang Quan Ren 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(1):m46-m49
In the two title complexes, (C24H20P)[Au(C3S5)2]·C3H6O, (I), and (C20H20P)[Au(C3S5)2], (II), the AuIII atoms exhibit square‐planar coordinations involving four S atoms from two 2‐thioxo‐1,3‐dithiole‐4,5‐dithiolate (dmit) ligands. The Au—S bond lengths, ranging from 2.3057 (8) to 2.3233 (7) Å in (I) and from 2.3119 (8) to 2.3291 (10) Å in (II), are slightly smaller than the sum of the single‐bond covalent radii. In (I), there are two halves of independent Ph4P+ cations, in which the two P atoms lie on twofold rotation axis sites. The Ph4P+ cations and [Au(C3S5)2]− anions are interspersed as columns in the packing. Layers composed of Ph4P+ and [Au(C3S5)2]− are separated by layers of acetone molecules. In (II), the [Au(C3S5)2]− anions and EtPh3P+ counter‐cations form a layered arrangement, and the [Au(C3S5)2]− anions form discrete pairs with a long intermolecular Au...S interaction for each Au atom in the crystal structure. 相似文献
11.
Ahmed O. Maslat Ibrahim Jibril Mahmoud Abussaud Emad H. Abd‐Alhadi Zuhair Hamadah 《应用有机金属化学》2002,16(1):44-50
A new series of bifunctional organoiron thio‐ and seleno‐terephthalate complexes — (η‐C5H5)Fe(CO)2ECO(C6H4)COX [E = S; X = C6H11NH, (C2H5)2N; and E = Se; X = P? CH3? C6H4? NH, C6H5? C2N2O? S, m? NO2? C6H4? CH?CH? COO] — has been synthesized via the organic transformation reactions of the terephthaloyl chloride precursors η‐(C5H5)Fe(CO)2ECO(C6H4)COCl with the desired nucleophiles. These new complexes were characterized by elemental analysis, IR and 1H NMR spectra. The above complexes, in addition to some other selected analogues, were tested for their antifungal, antibacterial and mutagenic activity. Our results show that all the selenium‐containing compounds have antifungal activity on Candida albicans and antibacterial effects against Bacillus subtilis and Staphylococcus aureus. Four of the six selenium‐containing derivatives exhibited growth inhibitory effects against Pseudomonas aeruginosa and/or Escherichia coli. Sulfur‐containing derivatives elicited activity against C. albicans, and each one of them showed activity against at least one of the bacterial strains that have been used in this investigation. Two selenium‐ and two sulfur‐containing derivatives showed mutagenic activity against one or more than one strain of the Salmonella typhimurium using the Ames test. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
12.
The photo‐induced substitution of a CO ligand has been used to prepare the halfsandwich complexes (η3‐C3H5)V(CO)4[P(C7H7)3] ( 1 ), (η5‐C5H5)V(CO)3[P(C7H7)3] ( 2 ), (η7‐C7H7)V(CO)2[P(C7H7)3] ( 3 ), (η6‐C6H3Me3)Cr(CO)2[P(C7H7)3] ( 4 ), and (η5‐C5H5)Mn(CO)2[P(C7H7)3] ( 7 ), in which the olefinic phosphane is coordinated as a conventional two‐electron ligand through the lone pair of electrons at phosphorus. Some analogues, which are permethylated at the aromatic ring ( 2* , 4* , 7* ), were included for comparison. Subsequent photo‐elimination of another CO group from 4 or 7 converts the olefinic phosphane into a chelating four‐electron ligand, leading to (η6‐C6H3Me3)Cr(CO)[P(C7H7)2(η2‐C7H7)] ( 5 ) and (η5‐C5H5)Mn(CO)[P(C7H7)2(η2‐C7H7)] ( 8 ), respectively. The η2‐coordinated double bond in 5 and 8 can be displaced by trimethylphosphite to give (η6‐C6H3Me3)Cr(CO)[P(C7H7)3][P(OMe)3] ( 6 ) and (η5‐C5H5)Mn(CO)[P(C7H7)3][P(OMe)3] ( 9 ). The 31P and 13C NMR spectra of all complexes are discussed, and X‐ray structure analyses for 2 and 8 are presented. Prolonged irradiation of 7 and 8 led to a di(cycloheptatrienyl)phosphido‐bridged dimer, {(η5‐C5H5)Mn(CO)[P(C7H7)2]}2( 10 ). 相似文献
13.
Murat Aydemir Akın Baysal Feyyaz Durap Bahattin Gümgüm Saim Özkar Leyla Tatar Yıldırım 《应用有机金属化学》2009,23(11):467-475
The reactions of thiophene‐2‐(N‐diphenylphosphino)methylamine, Ph2PNHCH2‐C4H3S, 1 and thiophene‐2‐[N,N‐bis(diphenylphosphino)methylamine], (Ph2P)2NCH2‐C4H3S, 2, with MCl2(cod) (M = Pd, Pt; cod = 1,5‐cyclooctadiene) or [Cu(CH3CN)4]PF6 yields the new complexes [M(Ph2PNHCH2‐C4H3S)2Cl2], M = Pd 1a, Pt 1b, [Cu(Ph2PNHCH2‐C4H3S)4]PF6, 1c, and [M(Ph2P)2NCH2‐C4H3S)Cl2], M = Pd 2a, Pt 2b, {Cu[(Ph2P)2NCH2‐C4H3S]2}PF6, 2c, respectively. The new compounds were isolated as analytically pure crystalline solids and characterized by 31P‐, 13C‐, 1H‐NMR and IR spectroscopy and elemental analysis. Furthermore, the solid‐state molecular structures of representative palladium and platinum complexes of bis(phosphine)amine, 2a and 2b, respectively, were determined using single crystal X‐ray diffraction analysis. The palladium complexes were tested as potential catalysts in the Heck and Suzuki cross‐coupling reactions. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
14.
Nigel T. Lucas Mark G. Humphrey 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(3):m171-m173
The two title compounds, [Mo2Ir2(C6H7)2(CO)10] and [Mo2Ir2(C9H13)2(CO)10]·0.5CH2Cl2, respectively, or collectively [Mo2Ir2(μ‐CO)3(CO)7(η5‐C5H5?nMen)2] (n = 1 or 4), have a pseudo‐tetrahedral Mo2Ir2 core geometry, an η5‐C5H5?nMen group ligating each Mo atom, bridging carbonyls spanning the edges of an MoIr2 face and seven terminally bound carbonyl groups. 相似文献
15.
Karel Mach Jií Kubita Ivana Císaov Petr tpni
ka 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(2):m116-m118
Reacting stoichiometric amounts of 1‐(diphenylphosphino)ferrocenecarboxylic acid and [Ti(η5‐C5HMe4)2(η2‐Me3SiC[triple‐bond]CSiMe3)] produced the title carboxylatotitanocene complex, [{μ‐1κ2O,O′:2(η5)‐C5H4CO2}{2(η5)‐C5H4P(C6H5)2}{1(η5)‐C5H(CH3)4}2FeIITiIII] or [FeTi(C9H13)2(C6H4O2)(C17H14P)]. The angle subtended by the Ti/O/O′ plane, where O and O′ are the donor atoms of the κ2‐carboxylate group, and the plane of the carboxyl‐substituted ferrocene cyclopentadienyl is 24.93 (6)°. 相似文献
16.
Tomáš Řezníček Libor Dostál Aleš Růžička Jaromír Vinklárek Martina Řezáčová Roman Jambor 《应用有机金属化学》2012,26(5):237-245
The intramolecularly coordinated phosphine and stibine ligands L1PPh2 ( 1 ), L2PPh2 ( 2 ) and L2SbPh2 ( 3 ) containing Y,C,Y‐chelating ligands, L1 = 2,6‐(tBuOCH2)2C6H4? and L2 = 2,6‐(Me2NCH2)2C6H4?, were prepared and characterized. The treatment of these ligands 1 , 2 , 3 with PtCl2 yielded complexes trans‐{[2,6‐(tBuOCH2)2C6H3]PPh2}2PtCl2 (4), cis‐{[2,6‐(Me2NCH2)2C6H3]PPh2}PtCl2 (5), and cis‐{[2,6‐(Me2NCH2)2C6H3]SbPh2}PtCl2 (6) as the result of different ability of the starting compounds 1 , 2 , 3 to complex platinum centre. Compounds 1 , 2 , 3 , 4 , 5 , 6 were characterized by 1H, 13C and 31P NMR spectroscopy and electrospray ionization mass spectrometry, and molecular structures of 3 , 4 , 5 , 6 were determined by X‐ray diffraction analysis. The substitution reactions of complexes 4 , 5 , 6 were also studied. The reaction of 5 and 6 with NaI yielded complexes {[2,6‐(Me2NCH2)2C6H3]PPh2}PtI2 ( 7 ) and {[2,6‐(Me2NCH2)2C6H3]SbPh2}PtI2 ( 8 ), while the same reaction of 4 with NaI did not proceed. As the compounds 7 and 8 structurally resemble cisplatin, complex {{[2‐(Me2NCH2)‐6‐(Me2NHCH2)C6H3]PPh2}PtCl2}+Cl? ( 9 ) was prepared as water‐soluble platinum complex. The cytotoxic effect of complex 9 was evaluated on human T‐lymphocytic leukemia cells MOLT‐4 (IC50 = 27.6 ± 1.8 µmol l?1) and human promyelocytic leukemia HL‐60 (IC50 = 55.9 ± 4.9 µmol l?1). Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
17.
Bipy, Phen, and P(C6H4CH2NMe2‐2)3 in the Synthesis of Cationic Silver(I) Complexes; the Solid‐State Structures of [P(C6H4CH2NMe2‐2)3]AgOTf and [Ag(phen)2]OTf The reaction of [P(C6H4CH2NMe2‐2)3]AgX ( 1a , X = OTf; 1b , X = OClO3) with equimolar amounts of LcapL ( 2a , LcapL = 2, 2′‐bipyridine, bipy; 2b , LcapL = 4, 4′‐dimethyl‐2, 2′‐bipyridine, bipy′; 2c , LcapL = 1, 10‐phenanthroline, phen) leads to the formation of the cationic complexes {[P(C6H4CH2NMe2‐2)3]Ag(LcapL)}+X— (LcapL = bipy: 3a , X = OTf; 3b , X = ClO4; LcapL = bipy′: 3c , X = OTf; 3d , X = ClO4; LcapL = phen: 3e , X = OTf; 3f , X = ClO4) in which the building blocks LcapL and P(C6H4CH2NMe2‐2)3 act as bidentate chelating ligands and are datively‐bound to the silver atom. Spectroscopic studies reveal that on the NMR time‐scale the phosphane group is dynamic with exchanging the respective Me2NCH2 built‐in arms. While complex 3e is stable in the solid‐state, it appeared that solutions of 3e start to decompose upon precipitation of colloidal silver when they are heated or irradiated with light, respectively. Appropriate work‐up of the reaction mixture allows the isolation of the phosphane P(C6H4CH2NMe2‐2)3 ( 5 ) along with [Ag(phen)2]OTf ( 4 ). The solid‐state structures of neutral 1a and cationic 4 are reported. Mononuclear 1a crystallizes in the monoclinic space group P21/c with the cell parameters a = 16.7763(2), b = 14.7892(2), c = 25.44130(10)Å, β = 106.1260(10), V = 6063.83(11)Å3 and Z = 4 with 8132 observed unique reflections (R1 = 0.0712), while 4 crystallizes in the monoclinic space group C2/c with the cell parameters a = 26.749(3), b = 7.1550(10), c = 26.077(3)Å, β = 113.503(2), V = 4576.8(10)Å3 and Z = 4 with 6209 observed unique reflections (R1 = 0.0481). The unit cell of 1a consists of two independent molecules. In both molecules the silver atom possesses a distorted tetrahedral coordination sphere and a boat‐like conformation for the six‐membered AgPNCH2C2/phenyl cycles is found. In 4 , as typical for 1a , the silver atom possesses the coordination number 4. The two phen ligands are tilted by 40.63°. The OTf group is acting as non‐coordinating counter ion. 相似文献
18.
Ramn Macías Simon A. Barrett Jonathan Bould Udo Drfler Josef Holub John D. Kennedy Mark Thornton‐Pett Bohumil tíbr 《Acta Crystallographica. Section C, Structural Chemistry》2001,57(5):520-522
Neutral 8‐(5‐iodo‐n‐pentyl)‐3‐(η5‐pentamethylcyclopentadienyl)‐arachno‐3‐rhoda‐7,8‐dithiaundecaborane, [Rh(C5H19B8IS2)(C10H15)], obtained from the [arachno‐7,8‐S2B9H10]? anion by treatment with I(CH2)5I followed by [Rh(C5Me5)Cl2]2 and N,N,N′,N′‐tetramethyl‐1,8‐diaminonaphthalene, has the 11‐vertex cluster geometry of [arachno‐7,8‐S2B9H10]?, but with an {Rh(C5Me5)} unit in the 3‐position instead of a {BH} unit, and with a –(CH2)5I chain attached exo to an S atom. 相似文献
19.
Unexpected Reduction of [Cp*TaCl4(PH2R)] (R = But, Cy, Ad, Ph, 2,4,6‐Me3C6H2; Cp* = C5Me5) by Reaction with DBU – Molecular Structure of [(DBU)H][Cp*TaCl4] (DBU = 1,8‐diazabicyclo[5.4.0]undec‐7‐ene) [Cp*TaCl4(PH2R)] (R = But, Cy, Ad, Ph, 2,4,6‐Me3C6H2 (Mes); Cp* = C5Me5) react with DBU in an internal redox reaction with formation of [(DBU)H][Cp*TaCl4] ( 1 ) (DBU = 1,8‐diazabicyclo[5.4.0]undec‐7‐ene) and the corresponding diphosphane (P2H2R2) or decomposition products thereof. 1 was characterised spectroscopically and by crystal structure determination. In the solid state, hydrogen bonding between the (DBU)H cation and one chloro ligand of the anion is observed. 相似文献
20.
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XVII [1] [Co(g5‐Me5C5)(g3‐tBu2PPCH–CH3)] from [Co(g5‐Me5C5)(g2‐C2H4)2] and tBu2P–P=P(Me)tBu2 [Co(η5‐Me5C5)(η3‐tBu2PPCH–CH3)] 1 is formed in the reaction of [Co(η5‐Me5C5)(η2‐C2H4)2] 2 with tBu2P–P 4 (generated from tBu2P–P=P(Me)tBu2 3 ) by elimination of one C2H4 ligand and coupling of the phosphinophosphinidene with the second one. The structure of 1 is proven by 31P, 13C, 1H NMR spectra and the X‐ray structure analysis. Within the ligand tBu2P1P2C1H–CH3 in 1 , the angle P1–P2–C1 amounts to 90°. The Co, P1, P2, C1 atoms in 1 look like a „butterfly”︁. The reaction of 2 with a mixture of tBu2P–P=P(Me)tBu2 3 and tBu–C?P 5 yields [Co(η5‐Me5C5){η4‐(tBuCP)2}] 6 and 1 . While 6 is spontaneously formed, 1 appears only after complete consumption of 5 . 相似文献