Generation and coupling of [Mn(dmpe)2(C triple bond CR)(C triple bond C)]* radicals producing redox-active C4-bridged rigid-rod complexes

The symmetric d(5) trans-bis-alkynyl complexes [Mn(dmpe)(2)(C triple bond CSiR(3))(2)] (R = Me, 1 a; Et, 1 b; Ph, 1 c) (dmpe = 1,2-bis(dimethylphosphino)ethane) have been prepared by the reaction of [Mn(dmpe)(2)Br(2)] with two equivalents of the corresponding acetylide LiC triple bond CSiR(3). The reactions of species 1 with [Cp(2)Fe][PF(6)] yield the corresponding d(4) complexes [Mn(dmpe)(2)(C triple bond CSiR(3))(2)][PF(6)] (R = Me, 2 a; Et, 2 b; Ph, 2 c). These complexes react with NBu(4)F (TBAF) at -10 degrees C to give the desilylated parent acetylide compound [Mn(dmpe)(2)(C triple bond CH)(2)][PF(6)] (6), which is stable only in solution at below 0 degrees C. The asymmetrically substituted trans-bis-alkynyl complexes [Mn(dmpe)(2)(C triple bond CSiR(3))(C triple bond CH)][PF(6)] (R = Me, 7 a; Et, 7 b) related to 6 have been prepared by the reaction of the vinylidene compounds [Mn(dmpe)(2)(C triple bond CSiR(3))(C=CH(2))] (R = Me, 5 a; Et, 5 b) with two equivalents of [Cp(2)Fe][PF(6)] and one equivalent of quinuclidine. The conversion of [Mn(C(5)H(4)Me)(dmpe)I] with Me(3)SiC triple bond CSnMe(3) and dmpe afforded the trans-iodide-alkynyl d(5) complex [Mn(dmpe)(2)(C triple bond CSiMe(3))I] (9). Complex 9 proved to be unstable with regard to ligand disproportionation reactions and could therefore not be oxidized to a unique Mn(III) product, which prevented its further use in acetylide coupling reactions. Compounds 2 react at room temperature with one equivalent of TBAF to form the mixed-valent species [[Mn(dmpe)(2)(C triple bond CH)](2)(micro-C(4))][PF(6)] (11) by C-C coupling of [Mn(dmpe)(2)(C triple bond CH)(C triple bond C*)] radicals generated by deprotonation of 6. In a similar way, the mixed-valent complex [[Mn(dmpe)(2)(C triple bond CSiMe(3))](2)(micro-C(4))][PF(6)] [12](+) is obtained by the reaction of 7 a with one equivalent of DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). The relatively long-lived radical intermediate [Mn(dmpe)(2)(C triple bond CH)(C triple bond C*)] could be trapped as the Mn(I) complex [Mn(dmpe)(2)(C triple bond CH)(triple bond C-CO(2))] (14) by addition of an excess of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) to the reaction mixtures of species 2 and TBAF. The neutral dinuclear Mn(II)/Mn(II) compounds [[Mn(dmpe)(2)(C triple bond CR(3))](2)(micro-C(4))] (R = H, 11; R = SiMe(3), 12) are produced by the reduction of [11](+) and [12](+), respectively, with [FeCp(C(6)Me(6))]. [11](+) and [12](+) can also be oxidized with [Cp(2)Fe][PF(6)] to produce the dicationic Mn(III)/Mn(III) species [[Mn(dmpe)(2)(C triple bond CR(3))](2)(micro-C(4))][PF(6)](2) (R = H, [11](2+); R = SiMe(3), [12](2+)). Both redox processes are fully reversible. The dinuclear compounds have been characterized by NMR, IR, UV/Vis, and Raman spectroscopies, CV, and magnetic susceptibilities, as well as elemental analyses. X-ray diffraction studies have been performed on complexes 4 b, 7 b, 9, [12](+), [12](2+), and 14.     

Facile [3+2] dimerization and formal dehydrogenative coupling mode of a cyanophenylphosphaallene

Due to a facile head-to-tail [3+2] dimerization, even a sterically demanding group such as the Mes^∗ (2,4,6-tri-tert-butylphenyl) group around the PCC moiety did not allow us to isolate 3-(4-cyanophenyl)-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaallene from the elimination reaction of 2-bromo-3-(4-cyanophenyl)-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaprop-1-ene with DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), and the corresponding 1,4-diphosphafulvene containing cyano groups was obtained and characterized. Theoretical studies on the [3+2] dimerization of phosphaallene characterize possible intermediates affording 1,4-diphosphafulvenes and also suggest the cyano group effect to facilitate the saturation of the PC double bonds. On the other hand, 1,2-bis(4-cyanophenyl)-3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene]cyclobutene was obtained from 2-bromo-3-(4-cyanophenyl)-3-trimethylsiloxy-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaprop-1-ene together with the 3-(4-cyanophenyl)-1-phosphaallene.     

Direct detection of polyynes formation from the reaction of ethynyl radical (C2H) with propyne (CH3-C[triple bond]CH) and allene (CH2=C=CH2)

The reactions of the ethynyl radical (C(2)H) with propyne and allene are studied at room temperature using an apparatus that combines the tunability of the vacuum ultraviolet radiation of the Advanced Light Source at Lawrence Berkeley National Laboratory with time-resolved mass spectrometry. The C(2)H radical is prepared by 193-nm photolysis of CF(3)CCH and the mass spectrum of the reacting mixture is monitored in time using synchrotron-photoionization with a dual-sector mass spectrometer. Analysis using photoionization efficiency curves allows the isomer-specific detection of individual polyynes of chemical formula C(5)H(4) produced by both reactions. The product branching ratios are estimated for each isomer. The reaction of propyne with ethynyl gives 50-70% diacetylene (H-C[triple bond]C-C[triple bond]C-H) and 50-30% C(5)H(4), with a C(5)H(4)-isomer distribution of 15-20% ethynylallene (CH(2)=C=CH-C[triple bond]CH) and 85-80% methyldiacetylene (CH(3)-C[triple bond]C-C[triple bond]CH). The reaction of allene with ethynyl gives 35-45% ethynylallene, 20-25% methyldiacetylene and 45-30% 1,4-pentadiyne (HC[triple bond]C-CH(2)-C[triple bond]CH). Diacetylene is most likely not produced by this reaction; an upper limit of 30% on the branching fraction to diacetylene can be derived from the present experiment. The mechanisms of polyynes formation by these reactions as well as the implications for Titan's atmospheric chemistry are discussed.     

Synthesis of Trideuteriomethyl 5-Deuterium-β-D-Mannopyranoside

Abstract

The title compound was prepared by first converting trideuteriomethyl 2,3,4-tri-O-benzyl-β-D-mannopyranoside to a 6-bromo-6-deoxy derivative which on elimination by using DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) or DBN (1,5-diazabi-cyclo[4.3.0]non-5-ene) gave a hex-5-enopyranoside derivative. The deuteroboration of the hex-5-enopyranoside followed by oxidation and subsequent deblocking produced trideuteriomethyl 5-deuterium-β-D-mannopyranoside.     

Unique cascade ring-opening/cyclization reaction of azlactones and DBU or DBN: Synthesis of new pyrrolam A analogues

1-Azabicyclo[3.3.0]oct-3-en-2-one derivatives were synthesized efficiently through the facile cascade reaction of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) with arylidene azlactones. This research provides a straightforward procedure for the synthesis of a novel class of multicyclic semi-alkaloids which shows good antimicrobial activity. Under catalyst-free, mild, and solventless condition, a wide range of fused tricyclic derivatives was obtained in high yields.     

Hetero-Diels-Alder Additions of α,β-Unsaturated-Acyl Cyanides. Part 3. Syntheses of 3-bromo-2-ethoxy-3,4-dihydro-2H-pyran-6-carbonitriles,and about their transformation to 2-ethoxy-2H-pyrans

Cycloadditions of the α,β-unsaturated-acyl cyanides 1–3 with (Z)-or (E)-1-bromo-2-ethoxyethene ( 4 ) may be performed at moderate temperatures and provide in good yields the 3-bromo-2-ethoxy-3,4-dihydro-2H-pyran-6-carbonitriles 5–7 , respectively (Scheme 1). Diastereoisomeric pairs of products result at room temperature merely from the ‘endo’- and ‘exo’-transition states; more complex mixtures appear above 60° as a consequence of (Z)/(E)-isomerization of 4 . The relative stability of the anomers of 5 and 6 is explored by treatment with BF₃·Et₂O. Acid alcoholysis (MeOH or EtOH) of 5 leads to acetals 9a , b of 4-bromo-5-oxopentanoate. Alkyl (2Z,4E)-5-ethoxypenta-2,4-dienoates 12 , 17 , and 20 , are formed in alcoholic alkoxide solutions from 5 , 6 , and 7 , respectively, which is compatible with the intermediacy of 2-alkoxy-2H-pyrans and their valence tautomers, α,β-unsaturatedacyl cyanides. Methoxide addition to the CN group competes with dehydrobromination in case of 5 ; it leads to 3-bromo-3,4-dihydro-2H-pyran-6-carboximidate 13 (ca. 50% at ?20°) which can be hydrolyzed to the methyl carboxylate 14 . DBU (1,8-diazabicyclo[5,4,0]undec-7-ene) in benzene converts 5 to 6-ethoxy-2-oxohexa-3,5-dienenitrile ( 11 ), the ring-opening product of an obviously unstable 2-ethoxy-2H-pyran; the same reagent dehydrobrominates 6 to 2-ethoxy-4-methyl-2H-pyran-6-carbonitrile ( 15 ). HBr Elimination from 7 takes place with great ease in presence of pyridine, or even during chromatography on alumina, and leads to the stable ethyl 6-cyano-2-ethoxy-2H-pyran-4-carboxylate ( 18 ); this dimerizes at room temperature to give a 1:3 mixture of tricyclic adducts ‘endo’- 21 and ‘exo’- 21 . The structure of the latter is established by an X-ray crystallographic analysis.     

Oxacalix[3]arene complexes with the ReI(CO)3 fragment

Oxacalix[3]arenes p-methyloxacalix[3]arene (L(1)), p-isopropyloxacalix[3]arene (L2), and p-ethoxycarbonyloxacalix[3]arene (L3) are able to bind the Re(I)(CO)3 moiety with two of their three phenol-O atoms and one of their ether-O atoms. The monoanionic complexes were isolated in the salts (DBUH)[Re(CO)3(L1H-2)].L1 (1) and (NEt4)[Re(CO)3(L2H-2)].L2.0.5 MeCN (2) (DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene). Over the course of its reaction with (NEt4)(2)[Re(CO)3Br(3)] and DBU, p-ethoxycarbonyloxacalix[3]arene decomposes to form [{Re(CO)3(L4H-2)}2] (3) {L4 = 1-(5-ethoxycarbonyl-2-hydroxy-3-hydroxymethyl-benzyl)-2,3,4,6,7,8,9,10-octahydro-pyrimido[1,2-a]azepin-1-ium. The expected monoanion [Re(CO)3(L3H-2)]- (4) was identified by 13C NMR and mass spectra.     

The simple solvent-free synthesis of 1H-quinazoline-2,4-diones using supercritical carbon dioxide and catalytic amount of base

Only supercritical carbon dioxide (scCO₂) as a reactant and a solvent, and catalytic amount of base (DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), DBN (1,5-diazabicyclo[4.3.0]non-5-ene), Dabco^® (1,4-diazabicyclo[2.2.2]octane), and triethylamine) afforded 1H-quinazoline-2,4-diones in good to excellent yields from 2-aminobenzonitriles. 6,7-Dimethoxy-1H-quinazoline-2,4-dione, which is a key intermediate of medicines (Prazosin, Bunazosin, and Doxazosin) was synthesized successfully in a 97% yield, using 0.1 equiv of DBU under scCO₂ (10 MPa) at 80 °C.     

Sonochemical fluorination of heterocyclic nitro compounds with Selectfluor™ (F-TEDA-BF4)

CH and CH₂ groups attached to a heterocycle and a nitro function were rapidly mono- or difluorinated by reaction with 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2,2,2]octane bis-tetrafluoroborate (Selectfluor) in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), preferably with ultrasonic irradiation.     

Ring Opening Three-Carbon Extension of 2-Carboethoxycyclo-Alkanones with 3-Bromo-1-(p-Tolylsulfonyl)Propene

Reaction with 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) of 2-[3-(p-tolylsulfonyl)-2-propenyl]-2-carboethoxycycloalkanones, derived from 2-carboethoxy-2-sodiocycloalkanones and 3-bromo-l-(p-tolylsulfonyl)propene, caused ring opening three-carbon extension in ethanol and three-carbon ring expansion in benzene to produce terminal dienes and cyclic dienes, respectively.     

Lithiated hydrocarbons, their conjugate bases, and corresponding radicals: a computational study of RLi (R = CH3, CH3CH2, CH2=CH, and HC triple bond C)

Organolithium compounds RLi (R = CH(3), CH(3)CH(2), CH(2)=CH, and HC(triple bond)C) and their corresponding hydrocarbons were fully optimized at the MP2/6-311+G(2df,2pd) level. Single-point energy calculations also were carried out at the CCSD(T) and B3LYP levels with the same triple split-valence basis set. Acidities, electron affinities, and bond dissociation energies are reported, and the following general results were found: (1) Alpha-lithio anions are ground-state triplet molecules. (2) Lithium is an acid-enhancing substituent. (3) Conjugate bases of organolithiums are stable with respect to electron loss and therefore are attractive targets for mass spectrometry investigations. (4) Lithium weakens alpha- and beta-C-H bonds, the latter by approximately 25 kcal mol(-1). Consequently, radical chemistry of lithiated compounds at remote sites is a promising area for exploration.     

Total Synthesis of (±)-Gelsemine

A complex molecular reorganization ( 1 → 2 ), a sequential anionic aza-Cope rearrangement and Mannich cyclization, and an unprecedented intramolecular Heck reaction of the tetrasubstituted double bond of a vinylogous carbamate are key steps in a new total synthesis of (±)-gelsemine ( 3 ). MOM=methoxymethyl, DBU=1,8-diazabicyclo[5.4.0]undec-7-ene.     

基于Barton-Zard反应的2-乙氧羰基-3-三氟甲基-4-甲基吡咯及其卟啉衍生物的改进合成

由2-乙氧羰基-3-硝基-1,1,1-三氟丁烷(1b)与异氰基乙酸乙酯发生Barton-Zard反应制备2-乙氧羰基-3-三氟甲基-4-甲基吡咯(1)的过程中,分别用K2CO3和乙醇代替有机碱1,8-二氮杂二环[5.4.0]十一碳-7-烯(DBU)和四氢呋喃溶剂,这种改进的Barton-Zard方法具有操作简便、试剂价廉易得、溶剂毒性低和产率更高等优点。 另外,在3-硝基-1,1,1-三氟-2-丁醇(1a)通过乙酰化反应转变为中间体1b的过程中,用沸腾温度下的甲苯溶液与乙酰氯代替浓硫酸催化下的酸酐反应体系;合成化合物1b的最优化的反应条件被确定为：乙酰氯与反应物1a之间的摩尔比为1.2∶1,反应时间为3～3.5 h。 又根据改进的卟啉合成法,在低温下用过量氢化铝锂还原吡咯1,将还原所得的尚未干燥或储存的粗产物α-羟甲基-三氟甲基-4-甲基吡咯(1c),立即在未经处理的三氯甲烷溶剂中,以三氟化硼·乙醚(BF3·OEt2)为催化剂进行四聚化反应,然后用2,3-二氯-5,6-二氰基-1,4-苯醌(DDQ)氧化,合成出含三氟甲基取代的卟啉衍生物2。 研究发现,由化合物1c制备产物2时,用BF3·OEt2取代p-TsOH作为催化剂,在确定的反应条件下,能够将产物2的收率由14%提高至50%。     

A microwave spectroscopic and quantum chemical study of 3-butyne-1-selenol (HSeCH2CH2C[triple bond]CH)

The microwave spectrum of 3-butyne-1-selenol has been studied by means of Stark-modulation microwave spectroscopy and quantum chemical calculations employing the B3LYP/aug-cc-pVTZ and MP2/6-311++G(3df,3pd) methods. Rotational transitions attributable to the H80SeCH2CH2C[triple bond]CH and H78SeCH2CH2C[triple bond]CH isotopologues of two conformers of this molecule were assigned. One of these conformers possesses an antiperiplanar arrangement for the atoms Se-C-C-C, while the other is synclinal and seems to be stabilized by the formation of a weak intramolecular hydrogen bond between the hydrogen atom of the selenol group and the pi electrons of the CC triple bond. The energy difference between these conformers was determined to be 0.2(5) kJ/mol by relative intensity measurements, and the hydrogen-bonded form was slightly lower in energy.     

Gas-phase rate coefficients for the reactions of nitrate radicals with (Z)-pent-2-ene, (E)-pent-2-ene, (Z)-hex-2-ene, (E)-hex-2-ene, (Z)-hex-3-ene, (E)-hex-3-ene and (E)-3-methylpent-2-ene at room temperature

Rate coefficients for reactions of nitrate radicals (NO3) with (Z)-pent-2-ene, (E)-pent-2-ene, (Z)-hex-2-ene, (E)-hex-2-ene, (Z)-hex-3-ene, (E)-hex-3-ene and (E)-3-methylpent-2-ene were determined to be (6.55 +/- 0.78)x 10(-13) cm3 molecule(-1) s(-1), (3.78 +/- 0.45)x 10(-13) cm3 molecule(-1) s(-1), (5.30 +/- 0.73)x 10(-13) cm(3) molecule(-1) s(-1), (3.83 +/- 0.47)x 10(-13) cm(3) molecule(-1) s(-1), (4.37 +/- 0.49)x 10(-13) cm(3) molecule(-1) s(-1), (3.61 +/- 0.40)x 10(-13) cm3 molecule(-1) s(-1) and (8.9 +/- 1.5)x 10(-12) cm3 molecule(-1) s(-1), respectively. We performed kinetic experiments at room temperature and atmospheric pressure using a relative-rate technique with GC-FID analysis. The experimental results demonstrate a surprisingly large cis-trans(Z-E) effect, particularly in the case of the pent-2-enes, where the ratio of rate coefficients is ca. 1.7. Rate coefficients are discussed in terms of electronic and steric influences, and our results give some insight into the effects of chain length and position of the double bond on the reaction of NO3 with unsaturated hydrocarbons. Atmospheric lifetimes were calculated with respect to important oxidants in the troposphere for the alkenes studied, and NO3-initiated oxidation is found to be the dominant degradation route for (Z)-pent-2-ene, (Z)-hex-3-ene and (E)-3-methylpent-2-ene.     

Dehydroiodination of 2-iodo-3-(polyfluoroalkyl)propoxymethyloxiranes

Dehydroiodination of 2-iodo-3-(polyfluoroalkyl)propoxymethyloxiranes upon treatment with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) afforded (polyfluoroalk-2-enyl)oxymethyloxiranes as E-and Z-isomers in ratio depending on the nature of the fluoroalkyl substituent. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2160–2162, November, 2007.     

The fixation of bis(2-pyridylimino)isoindolato (BPI) ligands to dendritic carbosilanes

Bis(2-pyridylimino)isoindolato (BPI) ligands, containing an alkynyl linker unit which allows their fixation to carbosilane dendrimers and dendrons, were synthesized by reaction of 4-nitrophthalodinitrile with 4-butynol giving the phthalodinitrile derivative containing the linker. These were subsequently reacted with two molar equivalents of 2-amino-4-methylpyridine and 2-amino-4-(t)butylpyridine yielding the respective BPI protioligands 2a and 2b. Lithiation with LDA and reaction with Si-Cl or Si-OTf (OTf=triflate) end groups in core or peripheral positions of dendritic carbosilanes gave the endodendrally and expdendrally functionalized dendrimers. Among these the first and second generation dendrimers [G-1](8-exo)-4-[C[triple bond, length as m-dash]CCH2CH2O]-10-MeBPI (8), [G-1]12-exo-4-[C[triple bond, length as m-dash]CCH2CH2O]-10-MeBPI (9) and [G-2](16-exo)-4-[C[triple bond, length as m-dash]CCH2CH2O]-10-MeBPI (10) were synthesized and fully characterized. The functional dendrimers were metallated by reaction with [(PhCN)2PdCl2] in dichloromethane to give the corresponding pallada-dendrimers.     

Synthesis, photophysics, electrochemistry, theoretical, and transient absorption studies of luminescent copper(I) and silver(I) diynyl complexes. X-ray crystal structures of [Cu3(micro-dppm)3(micro3-eta1-C triple bond CC triple bond CPh)2]PF6 and [Cu3(micro-dppm)3(micro3-eta1-C triple bond CC triple bond CH)2]PF6

A series of soluble trinuclear copper(I) and silver(I) complexes containing bicapped diynyl ligands, [M(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CR)(2)]PF(6) (M = Cu, R = Ph, C(6)H(4)-CH(3)-p, C(6)H(4)-OCH(3)-p, (n)C(6)H(13), H; M = Ag, R = Ph, C(6)H(4)-OCH(3)-p), has been synthesized and their electronic, photophysical, and electrochemical properties studied. The X-ray crystal structures of [Cu(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CPh)(2)]PF(6) and [Cu(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CH)(2)]PF(6) have been determined.     

Vanadium complexes of the N(CH2CH2S)3(3-) and O(CH2CH2S)2(2-) ligands with coligands relevant to nitrogen fixation processes

Vanadium(III) and vanadium(V) complexes derived from the tris(2-thiolatoethyl)amine ligand [(NS3)3-] and the bis(2-thiolatoethyl)ether ligand [(OS2)2-] have been synthesized with the aim of investigating the potential of these vanadium sites to bind dinitrogen and activate its reduction. Evidence is presented for the transient existence of (V(NS3)(N2)V(NS3), and a series of mononuclear complexes containing hydrazine, hydrazide, imide, ammine, organic cyanide, and isocyanide ligands has been prepared and the chemistry of these complexes investigated. [V(NS3)O] (1) reacts with an excess of N2H4 to give, probably via the intermediates (V(NS3)(NNH2) (2a) and (V(NS3)(N2)V(NS3) (3), the V(III) adduct [V(NS3)(N2H4)] (4). If 1 is treated with 0.5 mol of N2H4, 0.5 mol of N2 is evolved and green, insoluble [(V(NS3))n] (5) results. Compound 4 is converted by disproportionation to [V(NS3)(NH3)] (6), but 4 does not act as a catalyst for disproportionation of N2H4 nor does it act as a catalyst for its reduction by Zn/HOC6H3Pri2-2,6. Compound 1 reacts with NR1(2)NR2(2) (R1 = H or SiMe3; R2(2) = Me2, MePh, or HPh) to give the hydrazide complexes [V(NS3)(NNR2(2)] (R2(2) = Me2, 2b; R2(2) = MePh, 2c; R2(2) = HPh, 2d), which are not protonated by anhydrous HBr nor are they reduced by Zn/HOC6H3Pri2-2,6. Compound 2b can also be prepared by reaction of [V(NNMe2)(dipp)3] (dipp = OC6H3Pri2-2,6) with NS3H3. N2H4 is displaced quantitatively from 4 by anions to give the salts [NR3(4)][V(NS3)X] (X = Cl, R3 = Et, 7a; X = Cl, R3 = Ph, 7b; X = Br, R3 = Et, 7c; X = N3, R3 = Bu(n), 7d; X = N3, R3 = Et, 7e; X = CN, R3 = Et, 7f). Compound 6 loses NH3 thermally to give 5, which can also be prepared from [VCl3(THF)3] and NS3H3/LiBun. Displacement of NH3 from 6 by ligands L gives the adducts [V(NS3)(L)] (L = MeCN, nu CN 2264 cm-1, 8a; L = ButNC, nu NC 2173 cm-1, 8b; L = C6H11NC, nu NC 2173 cm-1, 8c). Reaction of 4 with N3SiMe3 gives [V(NS3)(NSiMe3)] (9), which is converted to [V(NS3)(NH)] (10) by hydrolysis and to [V(NS3)(NCPh3)] (11) by reaction with ClCPh3. Compound 10 is converted into 1 by [NMe4]OH and to [V(NS3)NLi(THF)2] (12) by LiNPri in THF. A further range of imido complexes [V(NS3)(NR4)] (R4 = C6H4Y-4 where Y = H (13a), OMe (13b), Me (13c), Cl (13d), Br (13e), NO2 (13f); R4 = C6H4Y-3, where Y = OMe (13g); Cl (13h); R4 = C6H3Y2-3,4, where Y = Me (13i); Cl (13j); R4 = C6H11 (13k)) has been prepared by reaction of 1 with R4NCO. The precursor complex [V(OS2)O(dipp)] (14) [OS2(2-) = O(CH2CH2S)2(2-)] has been prepared from [VO(OPri)3], Hdipp, and OS2H2. It reacts with NH2NMe2 to give [V(OS2)(NNMe2)(dipp)] (15) and with N3SiMe3 to give [V(OS2)(NSiMe3)(dipp)] (16). A second oxide precursor, formulated as [V(OS2)1.5O] (17), has also been obtained, and it reacts with SiMe3NHNMe2 to give [V(OS2)(NNMe2)(OSiMe3)] (18). The X-ray crystal structures of the complexes 2b, 2c, 4, 6, 7a, 8a, 9, 10, 13d, 14, 15, 16, and 18 have been determined, and the 51V NMR and other spectroscopic parameters of the complexes are discussed in terms of electronic effects.     

混杂[2, 3, 9, 10, 16, 17, 23, 24-八(庚基)酞菁][四(4-吡啶 基)卟啉]合钇 (III)二层配合物的合成及其谱学和电化学性质

用四(4-吡啶基)卟啉(H~2TPyP)与乙酰丙酮钇(III)[Y(acac)~3.H~2O]反应,生成单层配合物Y(TPyP)(acac)。将其与4,5-二(庚基)二氰基苯混和,后者在DBU催化下发生四聚反应,生成混杂[2,3,9,10,16,17,23,24-八(庚基)酞菁][四(4-吡啶基)卟啉]合钇(III)二层配合物Y(TPyP)[Pc(C~7H~1~5)~8]。该化合物用紫外-可见、近红外、红外及质谱等进行了表征,并用循环伏安法(CV)和差示脉冲法(DP)研究了其电化学性质。