Condensed isoquinolines. 37.* Heterocyclization using 3-(arylamino)- and 3-(hetarylamino)isoquinolin-1(2H)-ones

The reaction of 3-NHR-isoquinolin-1(2H)-ones (R = Ar) with aromatic aldehydes in the presence of Me3SiCl or in acetic acid leads to the formation of derivatives of dibenzo[b,f][1, 8]naphthyridin-5(6H)- one and benzo[f]isoquino[3,4-b][1, 8]naphthyridine-5,9(6H,7H)-dione. The reaction for R = Het in the presence of Me3SiCl gives derivatives of 5H-pyrido[1',2':1,2]pyrimido[4,5-c]isoquinolin-5-one, benzo[f]isoquinoline[3,4-b][1,8]naphthyridine-5,9[6H,7H]-dione, and derivatives of new heterocyclic systems, 5H-pyrazino[1',2':1,2]pyrimido[4,5-c]isoquinolin-5-one, 5H-[1,3]thiazolo[3',2':1,2]pyrimido- [4,5-c]isoquinolin-5-one, 5-H-benzo[f]pyrazolo[3,4-b][1,8]naphthyridin-5-one, and isoquino[3,4-b]- [1,5]naphthyridin-5(6H)-one. The effect of the structure of substituent R and nature of the substituent in the benzaldehydes on the structure of the reaction products was studied.     

Reaction of bis(trimethylsiloxy)phosphine with trimethylsilane

Bis(trimethylsilyl) [3-(trimethylsilyl)propyl]phosphonate and trimethylsilyl [3-(trimethylsilyl)propyl]-phosphinate are obtained by the reaction of bis(trimethylsiloxy)phosphine with trimethylallylsilane and converted into [3-(trimethylsilyl)propyl]phosphinic and [3-(trimethylsilyl)propyl]phosphonic acid, respectively, by the reaction with methanol.     

The photolysis of Chlorocarbonylbis(triphenylphosphine)iridium(I) in chloroform

Under 254 or 313 nm irradiation in chloroform, [IrCl(CO)(PPh3)2] is converted cleanly to [IrCl2(CO)H(PPh3)2] through the addition of HCl, produced photochemically. Under 254 nm irradiation, some of the reaction of [IrCl(CO)(PPh3)2] occurs by direct photolysis of chloroform, though a greater contribution arises from a reaction initiated through absorption of light by the metal complex. Under 313 nm irradiation, essentially all of the reaction is metal-initiated. The linear dependence of the reaction rate on light intensity and on the fraction of light absorbed by the Ir(I) complex as well as the lack of a deuterium isotope effect rule out a radical process. Instead it is proposed that an association complex between excited state [IrCl(CO)(PPh3)2] and CHCl3 leads to dissociation of a chlorine atom from CHCl3, yielding HCl after abstraction of a hydrogen from another CHCl3. HCl then adds to a ground state [IrCl(CO)(PPh3)2] complex.     

Mo(CO)6- and [Rh(CO)2Cl]2-catalyzed allenic cyclocarbonylation reactions of alkynones: efficient access to bicyclic dienediones

Allenyl alkynones are efficiently transformed into fused bicyclic dienediones via cyclocarbonylation reaction conditions. Mo(CO)6/DMSO reaction conditions result in the formation of a bicyclo[3.3.0]octenone ring system, and the [Rh(CO)2Cl]2-catalyzed reaction affords bicyclo[4.3.0]nonenone and bicyclo[5.3.0]decenone scaffolds.     

Tetra-, di-, and mononuclear copper(I) complexes containing (S,S)-iPr-pybox and (R,R)-Ph-pybox ligands

Tetranuclear [Cu4I4{(S,S)-iPr-pybox}2] (1) and dinuclear [Cu2Cl-{(S,S)-iPr-pybox}2][CuCl2] (2) copper(I) complexes have been synthesized by reaction of iPr-pybox with CuI and CuCl, respectively. Furthermore, dinuclear [Cu2(R-pybox)2][PF6]2 [R-pybox = (R,R)-Ph-pybox (3), (S,S)-iPr-pybox (4)] and mononuclear complexes [Cu(R-pybox)2][PF6] [R-pybox = (R,R)-Ph-pybox (5), (S,S)-iPr-pybox (6)] have been prepared by reaction of [Cu(MeCN)4][PF6] and the corresponding pybox. The structures of complexes 1-3 have been determined by X-ray diffraction analyses.     

含金属基团的四价锡化合物的合成和取代反应动力学

通式为[Fe(CO)~2Cp]~2Sn(Ar)Cl的化合物为一组新的化合物,由[Fe(CO)~2Cp]~2SnCl2与AgMgX反应合成.[Fe(CO)~2Cp]~2Sn(Ar)Cl与各种亲核试剂Y发生取代反应给出另一组新的化合物[Fe(CO)~2Cp]~2Sn(Ar)Y,其中[Fe(CO)~2Sn(p-MeC~6H~4)Br经X射线衍射分析确定结构.[Fe(CO)~2Cp]~2Sn(1,3,5-Me~3C~6H~3)Cl与NAS~2CNMe~2或KSCN在不同溶剂中的反应动力学表明,由于锡易形成高配位中间体,尽管锡上两个较大的金属基团带来一定空间障碍,反应仍主要按SN2机理进行.     

Synthesis and structure of diamido ether uranium(IV) and thorium(IV) halide "ate" complexes and their conversion to salt-free bis(alkyl) complexes

The high-yield synthesis, spectroscopic and structural determination of three new uranium(IV) and thorium(IV)ate complexes supported by three different diamido ether ligands are reported. The reaction of Li2[2,6-iPr2PhN(CH2CH2)]2O (Li2[DIPPNCOCN]) with 1 equiv. of UCl4 in THF generates [DIPPNCOCN]UCl3Li(THF)2(1), while reaction in toluene/ether gives salt-free [DIPPNCOCN]UCl2.1/2C7H8(2), which was identified by paramagnetically shifted 1H NMR. Reaction of 0.5 equiv. of {[tBuNON]UCl2}2([tBuNON]=[(CH3)3CN(Si(CH3)2)]2O2-) with 3.5 equiv. LiI in toluene and a minimal amount of THF results in [tBuNON]UI3Li(THF)2(3) and is very similar in structure to 1. {[MesNON]ThCl3Li(THF)}2(4), a dimeric complex with a Th2Li2Cl6 core, is prepared by reaction of Li2[2,4,6-Me3PhN(Si(CH3)2)]2O (Li2[MesNON]) with ThCl4 in THF. The analogous reaction in toluene did not yield the salt-free complex but rather a sterically crowded diligated compound, [MesNON]2Th (5), which was also structurally characterized. Complex 5 was prepared rationally by reacting 2 equiv. Li2[MesNON] with ThCl4 in toluene. The reaction of 1 and 3 with 2 equiv. of LiCH2Si(CH3)3 generates the stable, salt-free organoactinides [DIPPNCOCN]U(CH2Si(CH3)3)2(6) and [tBuNON]U(CH2Si(CH3)3)2(7). Complex 6 was structurally characterized. These reactions illustrate the viability of ate complexes as useful synthetic precursors.     

Synthesis and deprotonation of P-H-functionalised phosph(III)azanes; borohydride dependency on the formation of cis- or trans-[HP(mu-NtBu)2PNtBuH

The reaction of [ClP(muNtBu)2PNtBuH] (1) with LiBsBu3H yields trans-[HP(muNtBu)2PNtBuH] (2), by contrast, reaction with LiBEt3H yields cis-[HP(mu-NtBu)2PNtBuH] (3). Compounds and represent the first examples of P-H-functionalised cyclophosph(III)azanes. Deprotonation of with BnNa (Bn=benzyl) gives the first example of a secondary phosphine-functionalised cyclodiphosph(III)azane anion [HP(mu-NtBu)2PNtBu]- (4).     

A computational study of oxidation of ruthenium porphyrins via ORu(IV) and ORu(VI)O species

An unrestricted density functional theory (UDFT) was applied to study the oxidation of ruthenium porphyrins, [RuP], via an interaction with molecular oxygen. The important role of dimeric [RuP] complexes, i.e. [RuP]-O2-[RuP], in the oxidation mechanism and particular in the cleavage of O-O bond of molecular oxygen has been studied. Geometries and relative Gibbs free energies of the intermediate Ru-complexes, i.e. dimeric oxo-Ru-porphyrins and O2Ru(II)-(or O2- Ru(III))-, ORu(IV)- and ORu(VI)O-porphyrins, were evaluated along the proposed reaction pathway. The detailed thermodynamic data of the oxidation reaction [Ru(II)P] --> O[Ru(IV)P] --> O[Ru(VI)P]O and important aspects of the vibrational spectra of an oxo-[RuP] has been presented.     

Molybdenum(VI), (V) and (IV) complexes with chiral benzoin thiosemicarbazone

The chiral (ONS) dianionic Schiff base ligand benzoin thiosemicarbazone (H₂L) reacts with MoO₂(acac)₂ to give the polymeric complex [(MoO₂L) _n ] (1) (Type 1). The reaction of MoO₂L with pyridine (py), 3-picoline (3-pic) or 4-picoline (4-pic) gives [Mo^VIO₂LD] (D = py, 3-pic or 4-pic) (Type 1). Further, the reaction of [MoO₂L] or [MoO₂LD] with PPh₃ or reaction of [MoO₂L] with PPh₃ (plus bpy or phen, D) in the presence of donor reagents D gives [Mo^IVOL] or [Mo^IVOLD] (Type 2). On the other hand, the reaction of [MoO₂L] with hydrazides (zdhH₃) such as benzoylhydrazine (bhH₃), isonicotinoylhydrazine (inhH₃), nicotinoylhydrazine (nhH₃), salicyloylhydrazine (slhH₃) and thiosemicarbazide (tscH₃) produced non-oxo–diazenido complexes [MoL(zdh)] (Type 3). The complexes have been characterized by elemental analyses, molar conductance, magnetic moment, electronic, i.r. and e.s.r. spectroscopic measurements.     

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.     

Dendrimer interior functional group conversion and dendrimer metamorphosis--new approaches to the synthesis of oligo(dibenzyl sulfone) and oligo(phenylenevinylene) dendrimers

A series of [G1] to [G3]-oligo(dibenzylsulfide) dendrimers containing up to 21 interior dibenzylsulfide moieties was prepared as starting materials toward the syntheses of two new series of oligo(dibenzyl sulfone) and oligo(phenylenevinylene) dendrimers using two different dendrimer-to-dendrimer conversion strategies. The first strategy entailed the interior functionalization of the [G1] to [G3]-oligo(dibenzylsulfide)s to the corresponding [G1] to [G3]-oligo(dibenzyl sulfone)s via hydrogen peroxide oxidation. Successful conversions of up to 21 interior dibenzylsulfide moieties to the corresponding dibenzyl sulfone groups were demonstrated. The second involved the skeletal rearrangements, also named as dendrimer metamorphosis, of the [G1] and [G2]-oligo(dibenzyl sulfone) dendritic backbones to the corresponding [G1] and [G2]-oligo(phenylenevinylene)s dendrimers via the Ramberg-Backlund (RB) reaction. Up to nine RB rearrangements on a dendrimer skeleton were realized and the conversion efficiency of each single RB rearrangement reaction was found to be 96%.     

Towards Single-component Molecular Conductor [Ni(dmit)_2] by Charge Disproportionation:2[Ni(dmit)_2]~(-0.5)[Ni(dmit)_2]+[Ni(dmit)_2]~-

It was commonly thought that a molecular conductor or semiconductor should be composed of at least two components to make the conducting component in partially charged state. However, this idea became questionable by the recent report of the single-component molecular conductor [Ni(tmdt)2]1 as well as several reports about single-component molecular semiconductors such as [Ni(ptdt)2]2 and [Ni(C10H10S8)2]3. In fact, as early as 1985, [Ni(dmit)2] as a by-product in synthesizing TTF[Ni(dmit…     

Unsupported gold(I)-copper(I) interactions through eta1 Au-[Au(C6F5)2]- coordination to Cu+ Lewis acid sites

The reaction of the complex [Au2Ag2(C6F5)4)N[triple bond]CCH3)2]n (1) with 1 equiv of CuCl in the presence of 1 equiv of pyrimidine ligand leads to the formation of the heteronuclear Au(I)-Cu(I) organometallic polymer [Cu{Au(C6F5)2}(N[triple bond]CCH3)(mu2-C4H4N2)]n (2) through a transmetalation reaction. Complex 2 displays unprecedented unsupported Au(I)...Cu(I) interactions of [Au(C6F5)2]- units with the acid Cu(I) sites in a [Cu(N[triple bond]CCH3)(mu2-pyrimidine)]n+(n) polymeric chain. Complex 2 has a rich photophysics in solution and in the solid state.     

The first acetimine gold(I) and gold(III) complexes and the first acetonine complexes

Ketimino(phosphino)gold(I) complexes of the type [Au[NR=C(Me)R']L]X (X = ClO4, R = H, L = PPh3, R'=Me (la), Et (2a); L=PAr3 (Ar=C6H4OMe-4), R'=Me (1b), Et (2b); L=PPh3, R=R'=Me (3); X= CF3SO3 (OTf), L=PPh3, R=R'=Me (3'); R=Ar, R'=Me (4)) have been prepared from [Au(acac)L] (acac = acetyl acetonate) and ammonium salts [RNH3]X dissolved in the appropriate ketone MeC(O)R'. Complexes [Au(NH=CMe2)2]X (X = C1O4 (6), OTf (6')) were obtained from solutions of [Au(NH3)2]X in acetone. The reaction of 6 with PPN[AuCl2] or with PhICl2 gave [AuCl(NH=CMe2)] (7) or [AuCI2(NH=CMe2)2]ClO4 (8), respectively. Complex 7 was oxidized with PhICl2 to give [AuCl3(NH=CMe2)] (9). The reaction of [AuCl(tht)] (tht = tetrahydrothiophene), NaClO4, and ammonia in acetone gave [Au(acetonine)2]ClO4 (10) (acetonine = 2,2,4,4,6-pentamethyl-2,3,4,5-tetrahydropyrimidine) which reacted with PPh3 or with PPN[AuCl2] to give [Au(PPh3)(acetonine)]ClO4 (11) or [AuCl(acetonine)] (12), respectively. Complex 11 reacts with [Au(PPh3)(Me2CO)]ClO4 to give [(AuPPh3)2(mu-acetonine)](ClO4)2 (13). The reaction of AgClO4 with acetonine gave [Ag(acetonine)(OClO3)] (14). The crystal structures of [Au(NH2Ar)(PPh3)]OTf (5), 6' and 10 have been determined.     

Chelating or bridging Pd(II) and Pt(II) metalloligands from the functional phosphine ligand N-(diphenylphosphino)-1,3,4-thiadiazol-2-amine. New heterometallic Pd(II)/Pt(II) and Pt(II)/Au(I) complexes

The reaction of two equivalents of the functional phosphine ligand N-(diphenylphosphino)-1,3,4-thiadiazol-2-amine Ph2PNHC=NNCHS (2) with [PdCl2(NCPh)2] in the presence of NEt3 gives the neutral, P,N-chelated complex cis-[Pd(Ph2PN=CNN=CHS)2] ([Pd(2-H)2], 3b), which is analogous to the Pt(II) analogue cis-[Pt (Ph2PN=CNN=CHS)2] ([Pt(2-H)2], 3a) reported previously. These complexes function as chelating metalloligands when further coordinated to a metal through each of the CH-N atoms. In the resulting complexes, each endo-cyclic N donor of the thiadiazole rings is bonded to a different metal centre. Thus, the heterodinuclear palladium/platinum complexes cis-[Pt(Ph2PN=CNN=CHS)2PdCl2]([Pt(2-H)2·PdCl2], 4a) and cis-[Pd(Ph2PN=CNN=CHS)2PtCl2]([Pd(2-H)2·PtCl2], 4b) were obtained by reaction with [PdCl2(NCPh)2] and [PtCl2(NCPh)2], respectively. In contrast, reaction of 3a with [AuCl(tht)] occurred instead at the P-bound N atom, and afforded the platinum/digold complex cis-[Pt{Ph2PN(AuCl)=CNN=CHS}2] ([Pt(2-H)2(AuCl)2], 5). For comparison, reaction of 4a with HBF4 yielded cis-[Pt(Ph2PNH=CNN=CHS)2PdCl2](BF4)2([H24a](BF4)2, 6), in which the chelated PdCl2 moiety is retained. Complexes 3b, 4a·CH2Cl2, 4b·0.5C7H8, 5·4CHCl3 and 6 have been structurally characterized by X-ray diffraction.     

醋酸锰作用下二烯丙基叔胺与[60]富勒烯的自由基环加成反应

二烯丙基叔胺与[60]富勒烯在醋酸锰作用下发生自由基环加成反应,生成[60]富勒烯并吡咯烷衍生物.醋酸锰的用量和反应温度等因素对反应有一定影响.反应可能先由Mn(Ⅲ)与烯丙胺经单电子氧化产生自由基,再与[60]富勒烯加成并进一步环化.研究中得到的各产物的结构均通过波谱学方法表征.     

Promotion of phosphaalkyne cyclooligomerisation by a Sb(v) to Sb(iii) redox process

A high yield of the tetraphosphaladderene, anti-tetraphosphatricyclo[4.2.0.0(2,5)]octa-3,7-diene, is obtained from reaction of the zirconocene 1,3-diphosphabicyclo[1.1.0]butane with Ph(2)SbCl(3) in THF or CH(2)Cl(2). Exploration of the reaction pathway using density functional theory suggests that an envelope-type adduct of Ph(2)SbCl and 1,3-diphosphabicyclo[1.1.0]butane plays a pivotal role in the reaction. The zwitterionic character of this intermediate species allows it to act simultaneously as both an ene and an eneophile, and a symmetry-allowed bimolecular reaction leads to the tetraphosphaladderene species via a spirocyclic intermediate.     

Synthesis and reactivity of dichloroboryl complexes of platinum(II)

The reaction between [Pt(nbe)3] (nbe=norbornene), two equivalents of the phosphines PPh3, PMePh2 or PMe2Ph and 1 equivalent of BCl3 affords the platinum dichloroboryl species [PtCl(BCl2)(PPh3)2], [PtCl(BCl2)(PMePh2)2] and [PtCl(BCl2)(PMe2Ph)2]. All three complexes were characterised by X-ray crystallography and reveal that the boryl group lies trans to the chloride. With PMe3 as the phosphine, the complex [PtCl(BCl2)(PMe3)2] is isolated in high yield as a white crystalline powder although crystals suitable for X-ray crystallography were not obtained. Crystals were obtained of a product shown by X-ray crystallography to be the unusual dinuclear species [Pt2(BCl2)2(PMe3)4(micro-Cl)][BCl4] which reveals an arrangement in which two square planar platinum(II) centres are linked by a single bridging chloride which is trans to a BCl2 group on each platinum centre. The reaction of [PtCl(BCl2)(PMe3)2] with NEt3 or pyridine (py) affords the adducts [PtCl{BCl2(NEt3)}(PMe3)2] and [PtCl{BCl2(py)}(PMe3)2], respectively, both characterised spectroscopically. The reaction between [PtCl(BCl2)(PMe3)2] and either 4 equivalents of NHEt2 or piperidine (pipH) results in the mono-substituted boryl species [PtCl{BCl(NEt2)}(PMe3)2] and [PtCl{BCl(pip)}(PMe3)2], respectively, the former characterised by X-ray crystallography. Treatment of either [PtCl(BCl2)(PMe3)2] (in the presence of excess NEt3) or [PtCl{BCl(NEt2)}(PMe3)2] with catechol affords the B(cat) (cat=catecholate) derivative [PtCl{B(cat)}(PMe3)2] which is also formed in the reaction between [Pt(PMe3)4] and ClB(cat) and also from the slow decomposition of [Pt{B(cat)}2(PMe3)2] in dichloromethane over a period of months. The compound [Pt{B(cat)}2(PMe3)2] was prepared from the reaction between [Pt(PMe3)4] and B2(cat)2.     

Kinetics and mechanism of ruthenium(III)-catalysed oxidation of tellurium(IV) by alkaline diperiodatonickelate(IV)

The kinetics of Ru^III-catalysed oxidation of tellurium(IV) by alkaline diperiodatonickelate(IV) were studied spectrophotometrically using a rapid kinetic accessory. The reaction is a two stage process. In both the stages, the reaction is first-order with respect to [oxidant] and to [catalyst] with an apparent less than unit order, each in [substrate] and [alkali]. Periodate has a retarding effect on the reaction rate. A mechanism involving monoperiodatonickelate(IV) (MPN) as the reactive oxidant species is proposed. The data suggest that oxidation proceeds via formation of a complex between the active species of Ru^III and Te^IV, which then reacts with 1 mol of MPN in a slow step to yield the products. The reaction constants involved in the mechanism were evaluated. There is good agreement between the observed and calculated rate constants under varying experimental conditions for both the stages of reaction. The activation parameters for the slow step were calculated and discussed.