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1.
Prof. Dr. Michael I. Bruce Maryka Gaudio Benjamin C. Hall Brian K. Nicholson Gary J. Perkins Brian W. Skelton Allan H. White 《无机化学与普通化学杂志》2011,637(9):1207-1212
The preparation, characterisation and single‐crystal XRD molecular structure determinations of four complexes containing –CC–MLn end‐groups, namely Ru{C≡CFc′(I)}(dppe)Cp ( 1 ), the vinylidene [Os(=C=CH2)(PPh3)2Cp]PF6 ( 2 ), trans‐Pt(C≡CC6H4‐4‐C≡CPh){C≡CC6H4‐4‐C2Ph[Co2(μ‐dppm)(CO)4]}(PPh3)2 ( 3 ), and C6H4{μ3‐C2[AuRu3(CO)9(PPh3)]}2‐1,4 ( 4 ) are reported. In these compounds a range of –CC– environments is found, extending from the σ‐bonded alkynyl group in 1 to examples where the C2 unit interacts with either a proton (in vinylidene 2 ), by bridging a dicobalt carbonyl moiety (in 3 ) or the AuRu3 cluster in 4 . Changes in geometry are rationalised by considering the various bonding modes. 相似文献
2.
A series of ruthenium alkenylacetylide complexes trans-[Ru{C≡CC(=CH2)R}Cl(dppe)2] (R=Ph ( 1 a ), cC4H3S ( 1 b ), 4-MeS-C6H4 ( 1 c ), 3,3-dimethyl-2,3-dihydrobenzo[b]thiophene (DMBT) ( 1 d )) or trans-[Ru{C≡C-cC6H9}Cl(dppe)2] ( 1 e ) were allowed to react with the corresponding propargylic alcohol HC≡CC(Me)R(OH) (R=Ph ( A ), cC4H3S ( B ), 4-MeS-C6H4 ( C ), DMBT ( D ) or HC≡C-cC6H10(OH) ( E ) in the presence of TlBF4 and DBU to presumably give alkenylacetylide/allenylidene intermediates trans-[Ru{C≡CC(=CH2)R}{C=C=C(Me)}(dppe)2]PF6 ([ 2 ]PF6). These complexes were not isolated but deprotonated to give the isolable bis(alkenylacetylide) complexes trans-[Ru{C≡CC(=CH2)R}2(dppe)2] (R=Ph ( 3 a ), cC4H3S ( 3 b ), 4-MeS-C6H4 ( 3 c ), DMBT ( 3 d )) and trans-[Ru{C≡C-cC6H9}2(dppe)2] ( 3 e ). Analogous reactions of trans-[Ru(CH3)2(dmpe)2], featuring the more electron-donating 1,2-bis(dimethylphosphino)ethane (dmpe) ancillary ligands, with the propargylic alcohols A or C and NH4PF6 in methanol allowed isolation of the intermediate mixed alkenylacetylide/allenylidene complexes trans-[Ru{C≡CC(=CH2)R}{C=C=C(Me)}(dmpe)2]PF6 (R=Ph ([ 4 a ]PF6), 4-MeS-C6H4 ([ 4 c ]PF6). Deprotonation of [ 4 a ]PF6 or [ 4 c ]PF6 gave the symmetric bis(alkenylacetylide) complexes trans-[Ru{C≡CC(=CH2)R}2(dmpe)2] (R=Ph ( 5 a ), 4-MeS-C6H4 ( 5 c )), the first of their kind containing the dmpe ancillary ligand sphere. Attempts to isolate bis(allenylidene) complexes [Ru{C=C=C(Me)R}2(PP)2]2+ (PP=dppe, dmpe) from treatment of the bis(alkenylacetylide) species 3 or 5 with HBF4 ⋅ Et2O were ultimately unsuccessful. 相似文献
3.
Tetrakis(p‐tolyl)oxalamidinato‐bis[acetylacetonatopalladium(II)] ([Pd2(acac)2(oxam)]) reacted with Li–C≡C–C6H5 in THF with formation of [Pd(C≡C–C6H5)4Li2(thf)4] ( 1a ). Reaction of [Pd2(acac)2(oxam)] with a mixture of 6 equiv. Li–C≡C–C6H5 and 2 equiv. LiCH3 resulted in the formation of [Pd(CH3)(C≡C–C6H5)3Li2(thf)4] ( 2 ), and the dimeric complex [Pd2(CH3)4(C≡C–C6H5)4Li4(thf)6] ( 3 ) was isolated upon reaction of [Pd2(acac)2(oxam)] with a mixture of 4 equiv. Li–C≡C–C6H5 and 4 equiv. LiCH3. 1 – 3 are extremely reactive compounds, which were isolated as white needles in good yields (60–90%). They were fully characterized by IR, 1H‐, 13C‐, 7Li‐NMR spectroscopy, and by X‐ray crystallography of single crystals. In these compounds Li ions are bonded to the two carbon atoms of the alkinyl ligand. 1a reacted with Pd(PPh3)4 in the presence of oxygen to form the already known complexes trans‐[Pd(C≡C–C6H5)2(PPh3)2] and [Pd(η2‐O2)(PPh3)2]. In addition, 1a is an active catalyst for the Heck coupling reaction, but less active in the catalytic Sonogashira reaction. 相似文献
4.
The mononuclear amidinate complexes [(η6‐cymene)‐RuCl( 1a )] ( 2 ) and [(η6‐C6H6)RuCl( 1b )] ( 3 ), with the trimethylsilyl‐ethinylamidinate ligands [Me3SiC≡CC(N‐c‐C6H11)2]– ( 1a– ) and[Me3SiC≡CC(N‐i‐C3H7)2]– ( 1b– ) were synthesized in high yields by salt metathesis. In addition, the related phosphane complexes[(η5‐C5H5)Ru(PPh3)( 1b )] ( 4a ) [(η5‐C5Me5)Ru(PPh3)( 1b )] ( 4b ), and [(η6‐C6H6)Ru(PPh3)( 1b )](BF4) ( 5 ‐BF4) were prepared by ligand exchange reactions. Investigations on the removal of the trimethyl‐silyl group using [Bu4N]F resulted in the isolation of [(η6‐C6H6)Ru(PPh3){(N‐i‐C3H7)2CC≡CH}](BF4) ( 6 ‐BF4) bearing a terminal alkynyl hydrogen atom, while 2 and 3 revealed to yield intricate reaction mixtures. Compounds 1a / b to 6 ‐BF4 were characterized by multinuclear NMR (1H, 13C, 31P) and IR spectroscopy and elemental analyses, including X‐ray diffraction analysis of 1b , 2 , and 3 . 相似文献
5.
Prof. Dr. Michael I. Bruce Alexandre Burgun Guillaume Grelaud Martyn Jevric Brian K. Nicholson Brian W. Skelton Allan H. White Natasha N. Zaitseva 《无机化学与普通化学杂志》2011,637(10):1334-1340
Herein are described some continuing investigations into the reactions of cyano‐alkenes with diynyl‐ruthenium complexes which have resulted in the preparation and characterisation of diynyl‐ruthenium compounds Ru(C≡CC≡CR)(PP)Cp [R = Ph, PP = dppe; R = Fc, PP = dppf; R = CPh=CBr2, PP = (PPh3)2], together with the polycyanobutadienyls Ru{C≡CC[=C(CN)2]CR=CR′(CN)}(PP)Cp′ [R = Fc, (PP)Cp′ = (dppf)Cp; R = H, SiMe3, (PP)Cp′ = (dppe)Cp*] formed by [2 + 2]‐cycloaddition of the cyano‐alkenes to the outer C≡C triple bonds and subsequent ring‐opening reactions. Single‐crystal XRD molecular structure determinations of six complexes are reported. 相似文献
6.
The complexes [IrH(CO)(PPh3)3], trans-[IrCI(CO)- (PPh3)2], [RhH(PPh3)4], [Pd(PPh3)4], [Pt(trans-stilbene)(PPh3)2] and [Pt(η3-CH2-COCH2)-(PPh3)2] catalyse the rearrangement of Me3SiCH2C(O)CH2Cl to CH2?C(OSiMe3)-CH2Cl. 相似文献
7.
Michael R. Hall Rachel R. Steen Dr. Marcus Korb Dr. Alexandre N. Sobolev Dr. Stephen A. Moggach Dr. Jason M. Lynam Prof. Paul J. Low 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(32):7226-7234
Reactions of [Ru{C=C(H)-1,4-C6H4C≡CH}(PPh3)2Cp]BF4 ([ 1 a ]BF4) with hydrohalic acids, HX, results in the formation of [Ru{C≡C-1,4-C6H4-C(X)=CH2}(PPh3)2Cp] [X=Cl ( 2 a-Cl ), Br ( 2 a-Br )], arising from facile Markovnikov addition of halide anions to the putative quinoidal cumulene cation [Ru(=C=C=C6H4=C=CH2)(PPh3)2Cp]+. Similarly, [M{C=C(H)-1,4-C6H4-C≡CH}(LL)Cp ]BF4 [M(LL)Cp’=Ru(PPh3)2Cp ([ 1 a ]BF4); Ru(dppe)Cp* ([ 1 b ]BF4); Fe(dppe)Cp ([ 1 c ]BF4); Fe(dppe)Cp* ([ 1 d ]BF4)] react with H+/H2O to give the acyl-functionalised phenylacetylide complexes [M{C≡C-1,4-C6H4-C(=O)CH3}(LL)Cp’] ( 3 a – d ) after workup. The Markovnikov addition of the nucleophile to the remote alkyne in the cations [ 1 a–d ]+ is difficult to rationalise from the vinylidene form of the precursor and is much more satisfactorily explained from initial isomerisation to the quinoidal cumulene complexes [M(=C=C=C6H4=C=CH2)(LL)Cp’]+ prior to attack at the more exposed, remote quaternary carbon. Thus, whilst representative acetylide complexes [Ru(C≡C-1,4-C6H4-C≡CH)(PPh3)2Cp] ( 4 a ) and [Ru(C≡C-1,4-C6H4-C≡CH)(dppe)Cp*] ( 4 b ) reacted with the relatively small electrophiles [CN]+ and [C7H7]+ at the β-carbon to give the expected vinylidene complexes, the bulky trityl ([CPh3]+) electrophile reacted with [M(C≡C-1,4-C6H4-C≡CH)(LL)Cp’] [M(LL)Cp’=Ru(PPh3)2Cp ( 4 a ); Ru(dppe)Cp* ( 4 b ); Fe(dppe)Cp ( 4 c ); Fe(dppe)Cp* ( 4 d )] at the more exposed remote end of the carbon-rich ligand to give the putative quinoidal cumulene complexes [M{C=C=C6H4=C=C(H)CPh3}(LL)Cp’]+, which were isolated as the water adducts [M{C≡C-1,4-C6H4-C(=O)CH2CPh3}(LL)Cp’] ( 6 a–d ). Evincing the scope of the formation of such extended cumulenes from ethynyl-substituted arylvinylene precursors, the rather reactive half-sandwich (5-ethynyl-2-thienyl)vinylidene complexes [M{C=C(H)-2,5-cC4H2S-C≡CH}(LL)Cp’]BF4 ([ 7 a – d ]BF4 add water readily to give [M{C≡C-2,5-cC4H2S-C(=O)CH3}(LL)Cp’] ( 8 a – d )]. 相似文献
8.
Oxidative Addition Reactions of Complexed Phosphine and Arsine at Platinum(0) Complexes The reactions of E(SiMe3)3 with [W(CO)5thf] yield after alcoholysis in a one‐pot reaction the complexes [(CO)5WEH3] ( 1 ) (E = P( a ), As( b )). This procedure circumvents the direct use of gaseous phosphine and arsine, respectively. Complexes 1 react with [(C2H4)Pt(PPh3)2] in an oxidative addition type reaction to form the heterometallic complexes [(PPh3)2Pt(H){(μ‐EH2)W(CO)5}] (E = P( 2 ), As( 3 )). Complexes 2 and 3 were obtained as mixtures of their cis‐ and trans‐isomers, in which the contents of the trans‐isomer dominates. The products were comprehensively spectroscopically characterised, and the structures of the trans‐complexes 2 and 3 were determined by X‐ray crystal structure analysis. 相似文献
9.
Brenna K. Collins Dr. Melissa Clough Mastry Andreas Ehnbom Dr. Nattamai Bhuvanesh Prof. Dr. Michael B. Hall Prof. Dr. John A. Gladysz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(39):10021-10039
The dialkyl malonate derived 1,3-diphosphines R2C(CH2PPh2)2 (R= a , Me; b , Et; c , n-Bu; d , n-Dec; e , Bn; f , p-tolCH2) are combined with (p-tol3P)2PtCl2 or trans-(p-tol3P)2Pt((C≡C)2H)2 to give the chelates cis-(R2C(CH2PPh2)2)PtCl2 ( 2 a – f , 94–69 %) or cis-(R2C(CH2PPh2)2)Pt((C≡C)2H)2 ( 3 a – f , 97–54 %). Complexes 3 a – d are also available from 2 a – d and excess 1,3-butadiyne in the presence of CuI (cat.) and excess HNEt2 (87–65 %). Under similar conditions, 2 and 3 react to give the title compounds [(R2C(CH2PPh2)2)[Pt(C≡C)2]4 ( 4 a – f ; 89–14 % (64 % avg)), from which ammonium salts such as the co-product [H2NEt2]+ Cl− are challenging to remove. Crystal structures of 4 a , b show skew rhombus as opposed to square Pt4 geometries. The NMR and IR properties of 4 a – f are similar to those of mono- or diplatinum model compounds. However, cyclic voltammetry gives only irreversible oxidations. As compared to mono-platinum or Pt(C≡C)2Pt species, the UV-visible spectra show much more intense and red-shifted bands. Time dependent DFT calculations define the transitions and principal orbitals involved. Electrostatic potential surface maps reveal strongly negative Pt4C16 cores that likely facilitate ammonium cation binding. Analogous electronic properties of Pt3C12 and Pt5C20 homologs and selected equilibria are explored computationally. 相似文献
10.
The reaction of [(η5‐L3)Ru(PPh3)2Cl], where; L3 = C9H7 ( 1 ), C5Me5 (Cp*) ( 2 ) with acetonitrile in the presence of [NH4][PF6] yielded cationic complexes [(η5‐L3)Ru(PPh3)2(CH3CN)][PF6]; L3= C9H7 ([3]PF6) and L3 = C5Me5 ([4]PF6), respectively. Complexes [3]PF6 and [4]PF6 reacts with some polypyridyl ligands viz, 2,3‐bis (α‐pyridyl) pyrazine (bpp), 2,3‐bis (α‐pyridyl) quinoxaline (bpq) yielding the complexes of the formulation [(η5‐L3)Ru(PPh3)(L2)]PF6 where; L3 = C9H7, L2 = bpp, ([5]PF6), L3 = C9H7, L2 = bpq, ([6]PF6); L3 = C5Me5, L2 = bpp, ([7]PF6) and bpq, ([8]PF6), respectively. However reaction of [(η5‐C9H7)Ru(PPh3)2(CH3CN)][PF6] ([3]PF6) with the sterically demanding polypyridyl ligands, viz. 2,4,6‐tris(2‐pyridyl)‐1,3,5‐triazine (tptz) or tetra‐2‐pyridyl‐1,4‐pyrazine (tppz) leads to the formation of unexpected complexes [Ru(PPh3)2(L2)(CH3CN)][PF6]2; L2 = tppz ([9](PF6)2), tptz ([11](PF6)2) and [Ru(PPh3)2(L2)Cl][PF6]; L2 = tppz ([10]PF6), tptz ([12]PF6). The complexes were isolated as their hexafluorophosphate salts. They have been characterized on the basis of micro analytical and spectroscopic data. The crystal structures of the representative complexes were established by X‐ray crystallography. 相似文献
11.
R. W. Mason K. McGrouther P. R. R. Ranatunge‐Bandarage B. H. Robinson J. Simpson 《应用有机金属化学》1999,13(3):163-174
Toxicity, antitumour, platinum distribution, hepatotoxicity and histology data are presented for a series of ferrocenylamines: [(η‐C5H4(CH2)nNH2)FeCp] (n = 0,1) ( 1 , 2 ); [(η‐C5H4CH2NHPh)FeCp] ( 3 ); [(η‐C5H4CH2NMe2)FeCp] ( 4 ); {[η‐C5H4CH(Me)NMe2]FeCp} ( 5 ); [η‐C5H4CH2NMe2)2Fe] ( 6 ); {[1,2η‐C5H3(CHMeNMe2)(PPh2)]FeCp} ( 7 ); {[1,2η‐C5H3(CHMeNMe2)(PPh2)]Fe[η‐C5H4PPh2]} ( 8 ); and their complexes cis‐PtCl2L2 ( 9 ); trans ‐ Pt(L)(dmso)X2 ( 10 ); [σ ‐ (L)Pt(dmso)X] ( 11 , 12 ) {σ‐(L)[Pt(dmso)X]2} ( 13 ); [σ‐(L)PtP(OPh)3Cl] ( 14 ) (L = ferrocenylamine). The toxicity order is 1 – 3 ≫ 4 – 8 for the ferrocenylamines; the lower toxicity of tertiary amines may be due to protonation in vivo. Pt(II) complexes all show increased toxicity over the ligand. Liver, not kidney, damage is the norm from i.p. injection of 1 – 14 and detailed platinum distribution, blood serum and histology studies with 9 and 11 show that the platinum distribution does not correlate with liver dysfunction. Complexes 9 – 14 , but not 1 – 8 , were active against P‐388 mouse leukaemia tumour and cisplatin‐resistant sarcoma, but inactive against L‐1210 mouse leukaemia and B‐16 melanoma. Copyright © 1999 John Wiley & Sons, Ltd. 相似文献
12.
Carlo Bartocci Andrea Maldotti Silvana Sostero Orazio Traverso 《Journal of organometallic chemistry》1983,253(2):253-258
The photolysis of [L2Pt(C2H4)] (L = PPh3, P(p-C6H4CH3)3 complexes in halocarbon solvents (CH2Cl2, CH2Br2) gives C2H4 and the coordinatively unsaturated species [L2Pt]. Photolysis of platinum metallacycles [L2Pt(CH2)4] (L = PPh3, P(n-Bu)3) generates alkanes, alkenes and [L2Pt]. The [L2Pt] centers are very reactive, and under prolonged photolysis undergo oxidative addition of CH2Cl2 forming the trans-[L2Pt(CH2Cl)Cl] complexes. Under appropriately controlled conditions the trans complexes isomerize to cis species before bimolecular C2H4 elimination occurs and [L2PtCl2] is formed as the final product. The oxidative addition-reductive elimination mechanism is discussed on the basis of spin-trapping experiments, quantum yield values, and the sensitivity to radical inhibitors and to solvents. 相似文献
13.
Anthony F. Hill Richard A. Manzano 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(22):7435-7438
The reaction of the halocarbyne [W(≡CBr)(CO)2(Tp*)] (Tp*=hydrotris(3,5‐dimethylpyrazol‐1‐yl)borate) with trimethylsilyl‐butadiyne, mediated by [Pd(PPh3)4] and CuI, affords the first pentadiynylidyne complex [W(≡CC≡CC≡CSiMe3)(CO)2(Tp*)]. Desilylation provides a general route to heterobimetallic pentacarbido complexes, including [(Tp*)(CO)2W(μ‐C5)(PPh3)2Ru(η‐C5H5)] and [(Ph3P)2(CO)HIr{(μ‐C5)W(CO)2(Tp*)}2]. 相似文献
14.
Jonathan P. H. Charmant Juan Fornis Julio Gmez Elena Lalinde M. Teresa Moreno A. Guy Orpen Santiago Solano 《Angewandte Chemie (International ed. in English)》1999,38(20):3058-3061
Enhanced reactivity is shown by uncoordinated C≡C bonds in the proximity of a metal in phosphanylacetylene complexes. cis-[Pt(C6F5)2(thf)2] reacts with [M(C6F5)2(PPh2C≡CPh)2] (M=Pt, Pd) to form binuclear complexes containing the novel 2,3-bis(diphenylphosphanyl)-1,3-butadien-1-yl bridging ligand. Substitution of the solvent ligands with, for example, PPh2H (see picture) provides species that could be characterized by X-ray crystallography. 相似文献
15.
Hsuan‐Ting Lai Kun‐Hao Chen Yong‐Jie Li Cheng‐Hsien Wu Ching‐Han Hu Chia‐Her Lin Jui‐Hsien Huang 《中国化学会会志》2019,66(9):1041-1047
A series of ruthenium hydride compounds containing substituted bidentate pyrrole‐imine ligands were synthesized and characterized. Reacting RuHCl(CO)(PPh3)3 with one equivalent of [C4H3NH(2‐CH=NR)] in ethanol in the presence of KOH gave compounds {RuH(CO)(PPh3)2[C4H3N(2‐CH=NR)]} where trans‐Py‐Ru‐H 1, R = CH2CH2C6H9; cis‐Py‐Ru‐H 2, R = Ph‐2‐Me; and cis‐Py‐Ru‐H 3, R = C6H11. Heating trans‐Py‐Ru‐H 1 in toluene at 70°C for 12 hr resulted a thermal conversion of the trans‐Py‐Ru‐H 1 into its cis form, {RuH(CO)(PPh3)2[C4H3N(2‐CH=NCH2CH2C6H9)]} (cis‐Py‐Ru‐H 1) in very high yield. The 1H NMR spectra of trans‐Py‐Ru‐H 1, cis‐Py‐Ru‐H 2, cis‐Py‐Ru‐H 3, and cis‐Py‐Ru‐H 1 all show a typical triplet at ca. δ–11 for the hydride. The trans and cis form indicate the relative positions of pyrrole ring and hydride. The geometries of trans‐Py‐Ru‐H 1, cis‐Py‐Ru‐H 1, and cis‐Py‐Ru‐H 3 are relatively similar showing typical octahedral geometries with two PPh3 fragments arranged in trans positions. 相似文献
16.
Hydroboration of Alkynes with Zwitterionic Ruthenium–Borate Complexes: Novel Vinylborane Complexes 下载免费PDF全文
R. S. Anju Bijan Mondal Koushik Saha Subir Panja Babu Varghese Prof. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11393-11400
Building upon previous studies on the synthesis of bis(sigma)borate and agostic complexes of ruthenium, the chemistry of nido‐[(Cp*Ru)2B3H9] ( 1 ) with other ligand systems was explored. In this regard, mild thermolysis of nido‐ 1 with 2‐mercaptobenzothiazole (2‐mbzt), 2‐mercaptobenzoxazole (2‐mbzo) and 2‐mercaptobenzimidazole (2‐mbzi) ligands were performed which led to the isolation of bis(sigma)borate complexes [Cp*RuBH3L] ( 2 a – c ) and β‐agostic complexes [Cp*RuBH2L2] ( 3 a – c ; 2 a , 3 a : L=C7H4NS2; 2 b , 3 b : L=C7H4NSO; 2 c , 3 c : L=C7H5N2S). Further, the chemistry of these novel complexes towards various diphosphine ligands was investigated. Room temperature treatment of 3 a with [PPh2(CH2)nPPh2] (n=1–3) yielded [Cp*Ru(PPh2(CH2)nPPh2)‐BH2(L2)] ( 4 a – c ; 4 a : n=1; 4 b : n=2; 4 c : n=3; L=C7H4NS2). Mild thermolysis of 2 a with [PPh2(CH2)nPPh2] (n=1–3) led to the isolation of [Cp*Ru(PPh2(CH2)nPPh2)(L)] (L=C7H4NS2 5 a – c ; 5 a : n=1; 5 b : n=2; 5 c : n=3). Treatment of 4 a with terminal alkynes causes a hydroboration reaction to generate vinylborane complexes [Cp*Ru(R?C?CH2)BH(L2)] ( 6 and 7 ; 6 : R=Ph; 7 : R=COOCH3; L=C7H4NS2). Complexes 6 and 7 can also be viewed as η‐alkene complexes of ruthenium that feature a dative bond to the ruthenium centre from the vinylinic double bond. In addition, DFT computations were performed to shed light on the bonding and electronic structures of the new compounds. 相似文献
17.
Two ruthenium acetylide complexes [Ru]?C≡C?C≡C?C(OR)(C3H5)2 ( 2 , R=H and 2 a , R=CH3; [Ru]=Cp(PPh3)2Ru) each with two cyclopropyl rings were synthesized from TMS?C≡C?C≡C?C(OH)(C3H5)2 ( 1 ; TMS=trimethylsilyl). Treatments of 2 and 2 a with allyl halide in the presence of KPF6 afforded the vinylidene complexes 3 and 3 a , respectively. When NH4PF6 was used, instead of KPF6, additional ring‐opening reaction took place on one of the three‐membered ring. Treatment of [Ru]Cl with 1,3‐butadiyne ( 6 ), bearing an epoxide ring, afforded acetylide complex 7 with a furyl ring. Treatment of 2 a with Ph3CPF6 presumably afforded pentatetraenylidene complex {[Ru]=C=C=C=C=C(C3H5)2}[PF6] ( 10 ), which was not isolated. Additions of various alcohols in a solution of 10 generated a number of disubstituted allenylidene complexes {[Ru]=C=C=C(OR)?C=C(C3H5)2}[PF6] ( 11 ). Treatment of 11 with K2CO3 afforded the acetylide complex 12 bearing a carbonyl group, characterized by single X‐ray diffraction analysis. Addition of a primary amine to 10 caused cleavage of the farthermost C=C bond and several allenylidene complexes {[Ru]=C=C=C(Me)(NHR)}[PF6] ( 18 ) were isolated. 相似文献
18.
Christian Albrecht Christoph Wagner Kurt Merzweiler Tadeusz Lis Dirk Steinborn 《应用有机金属化学》2005,19(11):1155-1163
The platina‐β‐diketone [Pt2{(COMe)2H}2(µ‐Cl)2] ( 1 ) was found to react with monodentate phosphines to yield acetyl(chloro)platinum(II) complexes trans‐[Pt(COMe)Cl(PR3)2] (PR3 = PPh3, 2a ; P(4‐FC6H4)3, 2b ; PMePh2, 2c ; PMe2Ph, 2d ; P(n‐Bu)3, 2e ; P(o‐tol)3, 2f ; P(m‐tol)3, 2g ; P(p‐tol)3, 2h ). In the reaction with P(o‐tol)3 the methyl(carbonyl)platinum(II) complex [Pt(Me)Cl(CO){P(o‐tol)3}] ( 3a ) was found to be an intermediate. On the other hand, treating 1 with P(C6F5)3 led to the formation of [Pt(Me)Cl(CO){P(C6F5)3}] ( 3b ), even in excess of the phosphine. Phosphine ligands with a lower donor capability in complexes 2 and the arsine ligand in trans‐[Pt(COMe)Cl(AsPh3)2] ( 2i ) proved to be subject to substitution by stronger donating phosphine ligands, thus forming complexes trans‐[Pt(COMe)Cl(L)L′] (L/L′ = AsPh3/PPh3, 4a ; PPh3/P(n‐Bu)3, 4b ) and cis‐[Pt(COMe)Cl(dppe)] ( 4c ). Furthermore, in boiling benzene, complexes 2a – 2c and 2i underwent decarbonylation yielding quantitatively methyl(chloro)platinum(II) complexes trans‐[Pt(Me)Cl(L)2] (L = PPh3, 5a ; P(4‐FC6H4)3, 5b ; PMePh2, 5c ; AsPh3, 5d ). The identities of all complexes were confirmed by 1H, 13C and 31P NMR spectroscopy. Single‐crystal X‐ray diffraction analyses of 2a ·2CHCl3, 2f and 5b showed that the platinum atom is square‐planar coordinated by two phosphine ligands (PPh3, 2a ; P(o‐tol)3, 2f ; P(4F‐C6H4)3, 5b ) in mutual trans position as well as by an acetyl ligand ( 2a, 2f ) and a methyl ligand ( 5b ), respectively, trans to a chloro ligand. Single‐crystal X‐ray diffraction analysis of 3b exhibited a square‐planar platinum complex with the two π‐acceptor ligands CO and P(C6F5)3 in mutual cis position (configuration index: SP‐4‐3). Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
19.
《Journal of Coordination Chemistry》2012,65(15):1387-1393
Complexes of general formula [ReOX2{(C5H4N)CH(O)CH2(C5H4N)}] (X?=?Cl,?I) were prepared by reaction of trans-[ReOCl3(PPh3)2] and trans-[ReOI2(OEt)(PPh3)2] with cis-1,2-di-(2-pyridyl)ethylene (DPE) in ethanol and benzene in air. The coordinated DPE ligand undergoes addition of water at the ethylenic carbon atoms, and the (C5H4N)CH(O)CH2(C5H4N) moiety acts as a uninegative terdentate N,O,N-donor ligand. X-ray crystal structures of both complexes have been determined and show distorted octahedral geometry at the rhenium(V) centre. 相似文献
20.
Johan W. Gosselink Gerard van Koten Kees Vrieze Binne Zwanenburg Ben H.M. Lammerink 《Journal of organometallic chemistry》1979,179(4):411-419
Reactions of Pt(PPh3)4 with the sulfines, XYCSO, (X, Y = aryl, S-aryl, S-alkyl, Cl) yield coordination compounds of the type Pt(PPh3)2(XYCSO). Infrared, 31P and 1H NMR spectra reveal that in all cases the sulfine ligand is coordinated side-on via the CS π-bond (Pt—η2-CS). Reactions of Pt(PPh3)4 with either the E- or Z-isomer of (p-CH3C6H4)(CH3S)CSO yields the corresponding E- or Z-coordination compound, Pt(PPh3)2[E-(p-CH3C6H4)(CH3S)CSO] or Pt(PPh3)2[Z-(p-CH3C6H4)(CH3S)CSO], indicating that the configuration of the sulfine ligand is retained upon coordination to the Pt(PPh3)2 unit. The compounds Pt(PPh3)2(XYCSO), containing reactive CX and/or CY bonds (X, Y = S-aryl, S-alkyl, Cl), undergo a rearrangement in solution to give complexes of the type PtX(PPh3)2(YCSO). 相似文献