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1.
Falguni Basuli 《Journal of organometallic chemistry》2011,696(1):235-243
A series of reactivity studies of the carboamination pre-catalyst [Ti(NMe2)3(NHMe2)][B(C6F5)4] as well as the preparation of other catalysts are reported in this work. Treatment of [Ti(NMe2)3(NHMe2)][B(C6F5)4] with the aldimines Ar′NCHtol (Ar′ = 2,6-Me2C6H3, tol = 4-MeC6H4), and depending on the reaction conditions, results in isolation of [Me2NCHR′][B(C6F5)4] (1) or (Me2N)2CHtol, as well as the asymmetric titanium dimer [(Me2N)2(HNMe2)Ti(μ2-N[2,6-Me2C6H3])2Ti(NHMe2)(NMe2)][B(C6F5)4] (2). Protonation of CpTi(NMe2)3 and Cp∗Ti(NMe2)3 results in isolation of the salts, [CpTi(NMe2)2(NHMe2)][B(C6F5)4] (3) and [Cp∗Ti(NMe2)2(NHMe2)][B(C6F5)4] (4), respectively. Treatment of compounds 3 or 4 with H2N[2,6-iPr2C6H3] results in formation of the imido salts [CpTi(N[2,6-iPr2C6H3])(NHMe2)2][B(C6F5)4] (5) (58% yield) or [Cp∗Ti(N[2,6-iPr2C6H3])(NHMe2)2][B(C6F5)4] (6). When Ti(NMe2)4 is treated with [Et3Si][B(C6F5)4], the salt [Ti(NMe2)3(N[SiEt3]Me2)][B(C6F5)4] (7) is obtained, and treatment of the latter with [2,6-iPr2C6H3]NCHtol produces the imine adduct [Ti(NMe2)3(κ1-[2,6-iPr2C6H3]NCHtol)][B(C6F5)4] (8). The carboamination catalytic activity of complexes 2-7 was investigated and compared to [Ti(NMe2)3(NHMe2)][B(C6F5)4]. Likewise, a proposed mechanism to the active carboamination catalyst stemming from [Ti(NMe2)3(NHMe2)][B(C6F5)4] is described. 相似文献
2.
Sergey A. Belov Dmitrii P. Krut’ko Dmitrii A. Lemenovskii Judith A.K. Howard 《Journal of organometallic chemistry》2008,693(10):1912-1918
Novel half-sandwich [C9H5(SiMe3)2]ZrCl3 (3) and sandwich [C9H5(SiMe3)2](C5Me4R)ZrCl2 (R = CH3 (1), CH2CH2NMe2 (2)) complexes were prepared and characterized. The reduction of 2 by Mg in THF lead to (η5-C9H5(SiMe3)2)[η5:η2(C,N)-C5Me4CH2CH2N(Me)CH2]ZrH (7). The structure of 7 was proved by NMR spectroscopy data. Hydrolysis of 2 resulted in the binuclear complex ([C5Me4CH2CH2NMe2]ZrCl2)2O (6). The crystal structures of 1 and 6 were established by X-ray diffraction analysis. 相似文献
3.
Juri Ugolotti 《Journal of organometallic chemistry》2011,696(6):1184-1188
Treatment of R2Si(CC-SiMe3)2 [1a (Me), 1b (Ph)] with HB(C6F5)2 at low temperature (253 K (a), 273 K (b)) gives the -B(C6F5)2 substituted silacyclobutene products (4a,b) under kinetic control. Upon warming to room temperature they disappear to form the thermodynamically favoured isomeric silole derivatives (2a,b). Similar treatment of Me2Si(CC-R1)2 [5a (R1 = Ph), 5b (R1 = tert-butyl) with HB(C6F5)2 at room temperature gave the stable -B(C6F5)2 substituted silacyclobutene derivatives 6 and 7, respectively. Subsequent photolysis resulted in a Z- to E-isomerization of the substituted exocyclic CC double bonds in these products. The silacyclobutene derivative E-6 was characterized by an X-ray crystal structure analysis. 相似文献
4.
Robert K. Thomson 《Journal of organometallic chemistry》2011,696(25):3966-3973
Reaction of (C5Me5)2Lu(Me)(μ-Me)Li(THF)3 (2) with excess 12-crown-4 affords the new separated ion pair complex, [Li(12-crown-4)2][(C5Me5)2LuMe2] (3), in excellent yield. This complex reacts with 2,6-diisopropylaniline and phenylacetylene to give the methyl amide complex [Li(12-crown-4)2][(C5Me5)2Lu(Me)(NH-2,6-iPr2C6H3)] (4) and the bis(acetylide) complex [Li(12-crown-4)2][(C5Me5)2Lu(C≡C-Ph)2] (5), respectively. Attempts to promote methane loss from complexes 3 and 4 to generate a lutetium methylidene or imido complex, respectively, were unsuccessful. The ability of the bis(acetylide) complex 5 to act as a π-tweezer complex was also explored. Reaction between [Li(12-crown-4)2][(C5Me5)2Lu(C≡C-Ph)2] (5) and CuSPh gave only intractable lutetium products and the copper(I) species [Li(12-crown-4)2][Cu(C≡C-Ph)2] (8). The new lutetium complexes have been characterized by elemental analysis and NMR spectroscopy. Finally, the X-ray crystal structures of (C5Me5)2Lu(Me)(μ-Me)Li(THF)3 (2), [Li(12-crown-4)2][(C5Me5)2LuMe2] (3), [Li(12-crown-4)2][(C5Me5)2Lu(Me)(NH-2,6-iPr2C6H3)] (4), [Li(12-crown-4)2][(C5Me5)2Lu(C≡C-Ph)2] (5), and [Li(12-crown-4)2][Cu(C≡C-Ph)2] (8) are also reported. 相似文献
5.
William J. Evans Kevin A. Miller Wes R. Hillman Joseph W. Ziller 《Journal of organometallic chemistry》2007,692(17):3649-3654
The reductive reactivity of the (BPh4)1− ligand in pentamethylcyclopentadienyl [(C5Me5)2U][(μ-η2:η1-Ph)2BPh2] (1) was compared with that of the tetramethyl analog, [(C5Me4H)2U][(μ-η6:η1-Ph)(μ-η1:η1-Ph)BPh2] (2) using PhSSPh as a probe to determine if the mode of (BPh4)1− bonding affected the reduction. Both complexes act as two-electron reductants to form (C5Me4R)2U(SPh)2 [R = Me, 3; H, 4], but only in the R = H case could the product be crystallographically characterized. An improved synthesis of 1 from [(C5Me5)2UH]2 (5) and [Et3NH][BPh4] is also reported as well as its reaction with MeCN that provides another route to the unusual, parallel-ring, uranium metallocene [(C5Me5)2U(NCMe)5][BPh4]2 (6). 相似文献
6.
Rubén A. Machado María Cristina Goite Ysaura De Sanctis Antony J. Deeming Anibal Sierralta Teresa González 《Journal of organometallic chemistry》2007,692(4):894-902
The reaction of the labile compound [Re2(CO)8(CH3CN)2] with 2,3-bis(2-pyridyl)pyrazine in dichloromethane solution at reflux temperature afforded the structural dirhenium isomers [Re2(CO)8(C14H10N4)] (1 and 2), and the complex [Re2(CO)8(C14H10N4)Re2(CO)8] (3). In 1, the ligand is σ,σ′-N,N′-coordinated to a Re(CO)3 fragment through pyridine and pyrazine to form a five-membered chelate ring. A seven-membered ring is obtained for isomer 2 by N-coordination of the 2-pyridyl groups while the pyrazine ring remains uncoordinated. For 2, isomers 2a and 2b are found in a dynamic equilibrium ratio [2a]/[2b] = 7 in solution, detected by 1H NMR (−50 °C, CD3COCD3), coalescence being observed above room temperature. The ligand in 3 behaves as an 8e-donor bridge bonding two Re(CO)3 fragments through two (σ,σ′-N,N′) interactions. When the reaction was carried out in refluxing tetrahydrofuran, complex [Re2(CO)6(C14H10N4)2] (4) was obtained in addition to compounds 1-3. The dinuclear rhenium derivative 4 contains two units of the organic ligand σ,σ′-N,N′-coordinated in a chelate form to each rhenium core. The X-ray crystal structures for 1 and 3 are reported. 相似文献
7.
Wanda Ziemkowska Anna Kubiak Szymon Kucharski Robert Woźniak Romana Anulewicz-Ostrowska 《Polyhedron》2007
Reactions of Me5Al3[OC(C6H5)2C(C6H5)2O]2 (1) with alcohols ROH (R = Me, Et, tBu) in a 1:1 molar ratio afforded the compound Me2Al2[OC(C6H5)2C(C6H5)2O]2(C4H8O) (2) and a mixture of methylaluminum alkoxides. The alcohols acted as the factor formally eliminating a molecule of Me3Al (as a methylaluminum alkoxide) from compound 1. tBu3Al reacted with an equimolar amount of benzopinacol to form the monomeric complex tBuAl[OC(C6H5)2C(C6H5)2O](C4H8O) (3). Reactions of Me3Ga and Me3In with benzopinacol yielded trinuclear complexes Me5M3[OC(C6H5)2C(C6H5)2O]2 (4 (M = Ga), 5 (M = In)), isostructural to compound 1. In the presence of water and alcohols, compounds 4 and 5 underwent a decomposition reaction to benzopinacol and a mixture of metalloxanes and alkoxides. An unusual methylmethoxo indium benzopinacolate Me6In4[OC(C6H5)2C(C6H5)2O]2(OCH3)2 (6) was obtained in the reaction of benzopinacol with Me3In and Me2InOMe in a 1:1:1 molar ratio. Molecular structures of the compounds 3, 4 and 6 were determined by X-ray crystallography. 相似文献
8.
Grant D.W. Anderson Malcolm L.H. Green Ino C. Vei 《Journal of organometallic chemistry》2004,689(24):4407-4419
Reactions between [Fe(η-C5H5)(MeCO)(CO)(L)], L = PPh3 (1), PMe3 (2), PPhMe2 (3), PCy3 (4), CO (5), and B(C6F5)3 give new complexes [Fe(η-C5H5){MeCOB(C6F5)3}(CO)(L)] L = PPh3 (7), PMe3 (8), PPhMe2 (9), PCy3 (10), CO (11), where B(C6F5)3 coordinates selectively to the O-acyl groups. Hydrolysis of 7 gives [Fe(η-C5H5){HOB(C6F5)3}(CO)(PPh3)] (6). The X-ray structures of 6, 8 and 11 have been determined. Calculations, using density functional theory, demonstrate that the charge transfer to the acyl group on Lewis acid coordination is more significant in the σ than the π system. Both effects lead to a lengthening of the acyl C-O bond thus π populations cannot be inferred from the distance changes. 相似文献
9.
The reactions of [In(NEt2)3]2 and Sb(NEt2)3 with an equimolar amount of decafluorodiphenylamine (DFDPA, LH) lead to the indium or antimony amides [(C6F5)2NIn(NEt2)2]2 (1) and (C6F5)2NSb(NEt2)2 (2). Compound 2 rearranged further to give monofluoride Et2NSb(F)[N(o-Et2N-C6F4)(C6F5)] (3) and then difluoride F2Sb[N(o-Et2N-C6F4)2] (4). The hydrolysis of 4 gave free ligand HN(o-Et2N-C6F4)2 (5). Closely related HN(o-Me2N-C6F4)2 (6) was prepared from the reaction of Bi(NMe2)3 with DFDPA. The reactions of LiN(C6F5)2·THF with metal halides gave Sb[N(C6F5)2]3 (7), Me3Sb(Br)[N(C6F5)2] (8), Me3Sb(Cl)[N(C6F5)2] (9), Me3Sb[N(C6F5)2]2 (10), [Li(THF)2][In{N(C6F5)2}3Cl] (11). The X-ray structural investigations of 2 and 8 are presented. 相似文献
10.
The synthesis of bicyclic 6-hydroxy-6,8,8-dimethyl-5-aza-1-azonia-bicyclo[3.3.0]octa-1,3-diene chloride, [C6H5Me3N2(OH)]Cl, (5) by the HCl-catalyzed 1,4-cycloaddition of pyrazole (1) with mesityl oxide (4) is described. A proposed mechanism for the formation of 5 will be given. 相似文献
11.
Santiago Gómez-Ruiz Mariano Fajardo Antonio Otero 《Journal of organometallic chemistry》2007,692(14):3057-3064
The organo-tin compounds, Me2Sn(C5H4R-1)2 (R = Me (1), Pri (2), But (3), SiMe3 (4)) and Me2Sn(C5Me4R-1)2 (R = H (5), SiMe3 (6)), were prepared by the reaction of Me2SnCl2 with the lithium or sodium derivative of the corresponding cyclopentadiene. Compounds 1-6 have been characterized by multinuclear NMR spectroscopy (1H, 13C, 119Sn). In addition the molecular structures of 5 and 6 were determined by single crystal X-ray diffraction studies. The transmetalation reaction of 1-6 with ZrCl4 or [NbCl4(THF)2] gave the corresponding metallocene complexes in high yields. 相似文献
12.
Reactions of [Pt2(μ-Cl)2(C8H12OMe)2] (1) (C8H12OMe = 8-methoxy-cyclooct-4-ene-1-yl) with various anionic chalcogenolate ligands have been investigated. The reaction of 1 with Pb(Spy)2 (HSpy = pyridine-2-thiol) yielded a binuclear complex [Pt2(Spy)2(C8H12OMe)2] (2). A trinuclear complex [Pt3(Spy)4(C8H12OMe)2] (3) was isolated by a reaction between 2 and [Pt(Spy)2]n. The reaction of 1 with HSpy in the presence of NaOMe generated 2 and its demethylated oxo-bridged tetranuclear complex [Pt4(Spy)4(C8H12-O-C8H12)2] (4). Treatment of 1 with ammonium diisopropyldithiophosphate completely replaced C8H12OMe resulting in [Pt(S2P{OPri}2)2] (5), whereas non-rigid 5-membered chelating ligand, Me2NCH2CH2E−, produced mononuclear complexes [Pt(ECH2CH2NMe2)(C8H12OMe)] (E = S (6), Se (7)). These complexes have been characterized by elemental analyses, NMR (1H, 13C{1H}, 195Pt{1H}) and absorption spectroscopy. Molecular structures of 2, 3, 4, 5 and 7 were established by single crystal X-ray diffraction analyses. Thermolysis of 2, 6 and 7 in HDA gave platinum nanoparticles. 相似文献
13.
[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
14.
Yann Sarazin 《Journal of organometallic chemistry》2006,691(26):5680-5687
The new heteroleptic mercury(II) complex PhHgN(SiMe3)2(1) reacts with the strong Brønsted acid [H(OEt2)2][H2N{B(C6F5)3}2] with cleavage of a N-Si bond to give [C6H5Hg(H2NSiMe3)][H2N{B(C6F5)3}2] (2), a phenyl-mercury(II) cation stabilised by a primary amine and a non-coordinating counter-anion. Attempts to generate donor-free aryl mercury cations were not successful. The crystal structure of 2 · CH2Cl2 shows short π-bonding interactions between the metal and the phenyl ring of a neighbouring cation; the geometry about the mercury(II) atom is nearly linear. The X-ray structures of the new salts [H2N(SiMe3)2 · H3NSiMe3][B(C6F5)4]2 and [Et3O][H2N{B(C6F5)3}2] · CH2Cl2 are also presented. 相似文献
15.
N.G. Naumov A.V. Virovets D.Yu. Naumov V.E. Fedorov 《Journal of solid state chemistry》2004,177(6):1896-1904
The X-ray crystal structures of a series of new compounds (H3O)2[{Mn(H2O)1.5}3{Re6Se8(CN)6}2]·19H2O (1), (Me4N)2[{Co(H2O)1.5}3{Re6S8(CN)6}2]·13H2O (2), (Me4N)2[{Co(H2O)1.5}3{Re6Se8(CN)6}2]·3H2O (3), (Et4N)2[{Mn(H2O)2}3{Re6Se8(CN)6}2]·6.5H2O (4), (Et4N)2[{Ni(H2O)2}3{Re6S8(CN)6}2]·6.5H2O (5), and (Et4N)2[{Co(H2O)2}3{Re6S8(CN)6}2]·10H2O (6) are reported. All six compounds are isostructural crystallizing in cubic space group with four formulae per unit cell. For compounds 1, 3-5 the following parameters were found: (1) a=19.857(2) Å, R1=0.0283; (3 at 150 K) a=19.634(1) Å, R1=0.0572; (4) a=20.060(2) Å, R1=0.0288; (5) a=19.697(2) Å, R1=0.0224. The structures consist three-dimensional cyano-bridged framework formed by cyano cluster anions [Re6Q8(CN)6]4−, Q=S, Se and transition metal cations, M2+=Mn2+, Co2+, Ni2+. Water molecules and large organic cations Me4N+ and Et4N+ are included in cavities of this framework. Porosity of the framework, its ability to accommodate different cations and water molecules by little changes in the structure, as well as distortion of coordination framework under loss of water of crystallization is discussed. 相似文献
16.
The first one-dimensional (1-D) indiumphosphate chain, In2(HPO4)2(H2PO4)2F2·C4N2H12 (1), has been hydrothermally prepared using piperazine (PIP) as a template. The structure consists of infinite chains of trans,trans-corners-sharing InO4F2 octahedra with the adjacent octahedra being bridged by tetrahedral PO3(OH) and PO2(OH)2 units, which are H-bonded with amine groups of the organic cations. Interestingly, this macroanionic chain InP2O8H3F− is similar to that found in the mineral tancoite-like chains and has potential to further set up higher-dimensional networks. On heating 1 in the presence of additional phosphoric acid at 180 °C under hydrothermal condition, compound 2, In2(OH)(H2O)(PO4)2·H3O·H2O, possessed a 3-D structure building from the repetition of a secondary building unit is obtained. When 1 is heated with additional PIP, an unknown phase, compound 3 is formed. Finally, on treatment with another amine, such as diethylenetriamine or 1,4-diaminobutane, at 180 °C, 1, as a precursor, can convert into a previously known 3-D framework structure with 16-membered ring compound 4. Compounds 1 and 2 are determined by single-crystal X-ray diffraction. Furthermore, 1 is characterized by X-ray powder diffraction, IR spectroscopy, inductively coupled plasma analysis, thermogravimetric analysis and differential thermal analysis. 相似文献
17.
Paul W. Dickinson 《Journal of organometallic chemistry》2006,691(13):2883-2890
Treatment of hexabromoosmic acid, H2OsBr6, with 4 equiv. of tetramethylcyclopentadiene (C5Me4H2) in tert-butanol at reflux for 8 h affords the unusual salt [(C5Me4H)2OsBr]2[Os2Br8], 1, which is the bis(tetramethylcyclopentadienyl)bromoosmocinium(IV) salt of the octabromodiosmate(III) dianion. The brown color of the salt suggests that the anion adopts an eclipsed conformation (D4h symmetry) and this conclusion has been confirmed by a single-crystal X-ray diffraction experiment. The X-ray crystal structure indicates that the osmium atoms in the anion are disordered over two sites. The bromine atoms show no evidence of disorder and are disposed in a quasi-cubic arrangement; the two Os-Os vectors are almost exactly orthogonal to each other and each vector points toward a different pair of opposite square faces of the Br8 cube. The Os-Os bond distances are 2.219(5) and 2.229(1) Å; the average Os-Br distance in the anion is 2.417(2) Å. Treatment of [(C5Me4H)2OsBr]2[Os2Br8] with excess 1,5-cyclooctadiene in ethanol at gentle reflux for 3 h affords [(C5Me4H)2OsBr][Os2HBr4(cod)2], 2. An X-ray crystallographic study was carried out on a sample in which the cation was a mixture of [(C5Me4H)2OsBr+] and [(C5Me4H)2OsH+]. The results demonstrate that the anion adopts a confacial bioctahedral structure in which the hydride ligand and two bromides bridge between the two osmium centers. The CC bonds of the cod ligands are trans to the bridging bromide groups. The Os-Os bond distance in the anion is 2.874(1) Å. The average Os-Br distance is 2.596(2) Å for the bridging bromides and 2.565(2) Å for the terminal bromides. Compound 2 is the first example of an anionic diosmium complex containing a bridging hydride. The reaction of 1 with cod also results in the formation of bis(tetramethylcyclopentadienyl)osmocene, (C5Me4H)2Os, 3, which has been isolated and characterized. Treatment of (C5Me4H)2Os with 1.0 equiv. of HBF4 · Et2O affords the osmocinium salt [(C5Me4H)2OsH][BF4]. 相似文献
18.
Victor Wee Lin Ng 《Journal of organometallic chemistry》2004,689(20):3210-3217
The facile reaction of [CpCr(CO)3]2 (Cp = η5-C5H5) (1) with one mole equivalent of 2,2′-dithiodipyridine ((C5H4NS)2(SPy)2) at ambient temperature led to the isolation of dark brown crystalline solids of CpCr(CO)2(η2-SPy) (2) in ca. 72% yield. 2 undergoes quantitative conversion to CpCrCl2(η1-SPyH) (3) with HCl. The reaction 1 with one mole equivalent of 2-mercaptopyrimidine (C4H3N2SHHSPym) at ambient temperature led to the isolation of reddish-brown crystalline solids of CpCr(CO)2(η2-SPym) (4) and green solids of CpCr(CO)3H (5) in yields of ca. 42% and 46%, respectively. Reaction of 4 with HCl and subsequent workup in acetonitrile resulted in the cleavage of the thiolate ligand, giving the 15-electron chromium(III) species CpCrCl2(CH3CN) (6) and free 2-mercaptopyrimidine. The complexes 2-4 have been determined by single X-ray diffraction analysis. 相似文献
19.
Dmitrii P. Krut’ko Roman S. Kirsanov Maxim V. Borzov Andrei V. Churakov 《Journal of organometallic chemistry》2007,692(7):1465-1471
Half-sandwich [η5:η1-κN-C5Me4CH2-(2-C5H4N)]MCl3 (M = Ti (4), Zr (5)) and sandwich [η5-C5Me4CH2-(2-C5H4N)][η5-C5Me5]ZrCl2 (6) ring-peralkylated complexes have been prepared and characterized. Evidence of the intramolecular coordination of the side-chain pyridyl group both in 4 and 5 in solutions is provided by NMR spectroscopy data. Crystal structure of an adduct 5-py with one molecule of pyridine has been established by X-ray diffraction analysis. 相似文献
20.
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