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1.
The vinyl group in rans-[PtBr4{2-(CH2CH)py}(PEt3)] undergoes oxidation/metallation metallation ind amp solvents to give [H2·CO)py}(PEt3)]; the mechanisms of this reaction is discussed. Attempts to prepare this unusual complex from platinum(II) and platinum(IV) complexes containing 2-acetylpyridine were unsuccessful. 相似文献
2.
Michael Block Matthias Linnert Santiago Gmez-Ruiz Dirk Steinborn 《Journal of organometallic chemistry》2009,694(20):3353-3361
Lithiation of O-functionalized alkyl phenyl sulfides PhSCH2CH2CH2OR (R = Me, 1a; i-Pr, 1b; t-Bu, 1c; CPh3, 1d) with n-BuLi/tmeda in n-pentane resulted in the formation of α- and ortho-lithiated compounds [Li{CH(SPh)CH2CH2OR}(tmeda)] (α-2a–d) and [Li{o-C6H4SCH2CH2CH2OR)(tmeda)] (o-2a–d), respectively, which has been proved by subsequent reaction with n-Bu3SnCl yielding the requisite stannylated γ-OR-functionalized propyl phenyl sulfides n-Bu3SnCH(SPh)CH2CH2OR (α-3a–d) and n-Bu3Sn(o-C6H4SCH2CH2CH2OR) (o-3a–d). The α/ortho ratios were found to be dependent on the sterical demand of the substituent R. Stannylated alkyl phenyl sulfides α-3a–c were found to react with n-BuLi/tmeda and n-BuLi yielding the pure α-lithiated compounds α-2a–c and [Li{CH(SPh)CH2CH2OR}] (α-4a–b), respectively, as white to yellowish powders. Single-crystal X-ray diffraction analysis of [Li{CH(SPh)CH2CH2Ot-Bu}(tmeda)] (α-2c) exhibited a distorted tetrahedral coordination of lithium having a chelating tmeda ligand and a C,O coordinated organyl ligand. Thus, α-2c is a typical organolithium inner complex.Lithiation of O-functionalized alkyl phenyl sulfones PhSO2CH2CH2CH2OR (R = Me, 5a; i-Pr, 5b; CPh3, 5c) with n-BuLi resulted in the exclusive formation of the α-lithiated products Li[CH(SO2Ph)CH2CH2OR] (6a–c) that were found to react with n-Bu3SnCl yielding the requisite α-stannylated compounds n-Bu3SnCH(SO2Ph)CH2CH2OR (7a–c). The identities of all lithium and tin compounds have been unambiguously proved by NMR spectroscopy (1H, 13C, 119Sn). 相似文献
3.
Allan J. Canty Steven D. Fritsche Hong Jin R. Thomas Honeyman Brian W. Skelton Allan H. White 《Journal of organometallic chemistry》1996,510(1-2):281-286
The diorganoplatinum(II) complexes PtR2{(py)3COH} (R = Me, Ph; (py)3COH = tris(pyridin-2-yl)methanol) react with water in organic solvents to form diorgano(hydroxo)platinum(IV) cations [Pt(OH)R2{(py)3COH}]+, and the cation with R = Ph reacts with dilute nitric acid to form [PtPh2{(py)3COH}(OH2)]2+. The cation in [PtPh2{(py)3COH}(OH2)][NO3]2 · H2O has octahedral geometry with a Pt---O bond distance of 2.04(1) Å. The higher trans influence of phenyl than aqua ligands is reflected in the Pt---N bond distances: 2.14(2) and 2.17(1) Å trans to the phenyl groups, and 1.99(2) Å trans to the aqua ligand. 相似文献
4.
Stephan Back Martin Lutz Anthony L. Spek Heinrich Lang Gerard van Koten 《Journal of organometallic chemistry》2001,620(1-2)
A series of homodinuclear Pt compounds containing the anionic, potentially terdentate NCN ligand (NCN=[C6H3(Me2NCH2)2-2,6]−) or its 4-ethynyl derivative were prepared. The two platinum centres are linked together in two different fashions: (i) directly linked by an ethynyl or diethynylphenyl group (head-to-head) and (ii) indirectly bonded by a ethynyl- or butadiynyl-linked bis-NCN ligand (tail-to-tail). The reaction of the head-to-head σ,σ′-ethynylide complex {Pt}CC{Pt} ({Pt}=[Pt(C6H3{CH2NMe2}2-2,6)]+) with [CuCl]n yields {Pt}Cl and [Cu2C2]n, while with [Cu(NCMe)4][BF4] a Cu(I) bridged complex was formed: [(η2-{Pt}CC{Pt})2Cu][BF4]. The results of cyclic voltammetry experiments reveal that both connection modes of the two platinum centres lead to electrochemically independent Pt–NCN units. The X-ray crystal structure analysis of the neutral, tail-to-tail bridging butadiyne bis-NCNH ligand [C6H3(CH2NMe2)-1,3-(CC)-5]2 is reported. 相似文献
5.
Alkynes react with the benzalacetone complex [C6H5 CH=CHC(O)CH3]Fe(CO)3 in boiling benzene to give nearly exclusively the corresponding tricarbonylferrole—iron tricarbonyl derivatives. 相似文献
6.
Four platinum(II) complexes of the general formula cis‐[Pt{(Ferr)2PhP}(DMSO)X2], where X2 = Cl2, C2O4, O2(CO)2(C6H11)2 and O2(CO)2CCH2CH2CH2, have been synthesized andcharacterized physicochemically and spec‐troscopically as the first heterobimetallic platinum(II) complexes with the ligand diferrocenylphenylphosphine (Ferr = ferrocenyl). These complexes were tested in vitro against leukaemia cell line P388 using the MTT assay. The results obtained were compared with those of cisplatin, carboplatin, oxaliplatin and 5‐fluorouracil. Copyright © 1999 John Wiley & Sons, Ltd. 相似文献
7.
Treatment of the osmabenzene [Os{CHC(PPh3)CHC(PPh3)CH} Cl2(PPh3)2]Cl ( 1 ) with excess 8‐hydroxyquinoline produces monosubstituted osmabenzene [Os{CH C(PPh3) CHC(PPh3)CH}(C9H6NO)Cl(PPh3)]Cl ( 2 ) or disubstituted osmabenzene [Os{CHC(PPh3)CHC(PPh3)CH} (C9H6NO)2]Cl ( 3 ) under different reaction conditions. Osmabenzene 2 evolves into cyclic η2‐allene‐coordinated complex [Os{CH?C(PPh3)CH=(η2‐C?CH2)}(C9H6NO)(PPh3)2]Cl ( 4 ) in the presence of excess PPh3 and NaOH, presumably involving a P? C bond cleavage of the metallacycle. Reaction of 4 with excess 8‐hydroxyquinoline under air affords the SNAr product [(C9H6NO)Os{CHC(PPh3)CHCHC} (C9H6NO)(PPh3)]Cl ( 5 ). Complex 4 is fairly reactive to a nucleophile in the presence of acid, which could react with water to give carbonyl complex [Os{CH?C(PPh3)CH?CH2}(C9H6NO) (CO)(PPh3)2]Cl ( 6 ). Complex 4 also reacts with PPh3 in the presence of acid and results in a transformation to [Os {CHC(PPh3)CHCHC}(C9H6NO)Cl (PPh3)2]Cl ( 7 ) and [Os{CH?C(PPh3) CH=(η2‐C?CH(PPh3))}(C9H6NO) Cl(PPh3)]Cl ( 8 ). Further investigation shows that the ratio of 7 and 8 is highly dependent on the amount of the acid in the reaction. 相似文献
8.
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
9.
《Journal of Coordination Chemistry》2012,65(3-4):305-309
Abstract The reaction of [MoCl(GeCl3)(CO)3(NCMe)2] with an equimolar quantity of L?L {L?L = 2,2′-bipy, 1,10-phen, Ph2P(CH2)nPPh2 (n = 1 or 2)} in CH2Cl2 at room temperature gave either [MoCl(GeCl3)(CO)3(L?L)] (L?L = 2,2′-bipy or 1,10-phen) (1 and 2) or [MoCl(GeCl3)(CO)2 (NCMe)(L?L)]{L?L = Ph2P(CH2)nPPh2 (n = 1 or 2) (3 or 4), respectively. Equimolar quantities of [MoCl(GeCl3)(CO)2(NCMe){Ph2P(CH2)PPh2}] (3) and L?L {L?L = 2,2′-bipy or Ph2P(CH)2PPh2} react in CH2Cl2 at room temperature to afford the cationic complexes [Mo(GeCl3)(CO)2{Ph2P(CH2) PPh2}(L?L)]Cl (5 and 6) in good yield. The cationic nature of 6 was established by chloride exchange by reacting Na[BPh4] with 6 in acetonitrile to give the tetraphenylborate complex [Mo(GeCl3)(CO)2{Ph2P(CH2)PPh2}2][BPh4] (7). Reaction of equimolar quantities of [MoCl(GeCl3) (CO)3(NCMe)2] and PhP(CH2CH2PPh2)2 in CH2Cl2 at room temperature afforded the dicarbonyl complex [MoCl(GeCl3)(CO)2{PhP(CH2CH2PPh2)2}] (8) in good yield. 相似文献
10.
《Journal of organometallic chemistry》1987,333(2):253-262
The isomeric butadiene compounds 1,1- and 1,2-[Os3(C4H6)(CO)10] and the acetonitrile compound 1,2-[Os3(CO)10(MeCN)2] react with the diphosphines Ph2P(CH2)nPPh2 (n = 2, 3 or 4) to give separable isomers of [Os3(CO)10(diphosphine)] in which the diphosphine is either bridging or chelating, whereas dppm (n = 1) gives only the 1,2-isomer. The mono-acetonitrile compound [Os3-(CO)11(MeCN)] reacts to give two series of compounds: [Os3(CO)11(diphosphine)], containing one coordinated and one free phosphorus atom, and [Os6(CO)22(diphosphine)] with two Os3(CO)11 groups bridged by the diphosphine. The triphosphine, Ph2PCH2CH2PPhCH2CH2PPh2 (triphos), reacts similarly to give two separable isomers of [Os3(CO)11(triphos)] and two inseparable isomers of [Os6(CO)22(triphos)]. Whereas [Os3(CO)11(dppm)] readily undergoes decarbonylation to give 1,2-[Os3(CO)10(dppm)], other compounds of the type [Os3(CO)11(diphosphine)] are not decarbonylated under the same conditions, but react with Me3NO to give the 1,2-but not the 1,1-isomers of [Os3(CO)10(diphosphine)]. 相似文献
11.
Reactions of copper(I) halides with racemic 2,2′-bis(diphenylphosphano)-1,1′-binaphthyl (rac-binap) in 1:1 molar ratio afforded mononuclear complexes of the type [CuX(rac-binap)] (X = Cl, Br, I) which, on further treatment with 1 equiv. of pyridine-2-thione (py2SH), pyrimidine-2-thione (pymtH) or 4,6-dimethyl-pyrimidine-2-thione (dmpymtH) gave rise to the formation of mixed-ligand complexes of the formula [CuX(rac-binap)(thione)]. The molecular structures of [CuBr(rac-binap)(py2SH)] · 2CH2Cl2, [CuBr(rac-binap)(py2SH)] · CH2Cl2 and [CuBr(rac-binap)(dmpymtH)] · CH2Cl2 have been established by single-crystal X-ray diffraction. Each of the complexes features a distorted tetrahedral copper(I) center with the phosphane acting in a chelating fashion. The complexes are strongly luminescent in the solid state at ambient temperature. Unusually, the [CuBr(rac-binap)(py2SH)] · 2CH2Cl2 molecules crystallise in a chiral space group with independent S- and R-enantiomers in the asymmetric unit. 相似文献
12.
Mohammad El-khateeb Hassan Abul-Futouh Hadil Alshurafa Helmar Görls Wolfgang Weigand 《应用有机金属化学》2020,34(11):e5940
Substitution of carbonyl ligands of the hydrogenase model complex [Fe2(μ-SeCH2CH(Me)CH2Se-μ)(CO)6] ( A ), by 1,1′-bis (diphenylphosphino)ferrocene (dppf), 1,2-bis (diphenylphosphino)benzene (dppbz) or 1,2-bis (diphenylphosphino)acetylene (dppac) is investigated. It is found that the reaction product depends on the diphosphine used. In the case of dppf, the product is an intramolecular bridged disubstituted complex [Fe2{μ-SeCH2CH(Me)CH2Se-μ}(CO)4{μ,κ1,κ1(P,P)-dppf}] ( 1 ), while the dppac-reaction produces an intermolecular bridged tetra-iron model [Fe2{μ-SeCH2CH(Me)CH2Se-μ}(CO)5]2{μ,κ1,κ1(P,P)-dppac} ( 2 ). However, the dppbz-reaction gives [Fe2{μ-SeCH2CH(Me)CH2Se-μ}(CO)4{κ2(P,P)-dppbz}] ( 3 ) in which the dppbz ligand is bonded to one Fe atom in a chelated manner. The newly prepared complexes ( 1 – 3 ) have been characterized by elemental analysis, IR, 1H-, 13C{H}-, 31P{H}-, 77Se{H}-NMR spectroscopy and X-ray structure determination. The electrochemical behavior of 2 and 3 , in absence and presence of acid, is described by cyclic voltammetric measurements in CH2Cl2. 相似文献
13.
Hong Zhang Dr. Ran Lin Guangning Hong Tongdao Wang Ting Bin Wen Prof. Dr. Haiping Xia Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(23):6999-7007
The reactions of phosphonium‐substituted metallabenzenes and metallapyridinium with bis(diphenylphosphino)methane (DPPM) were investigated. Treatment of [Os{CHC(PPh3)CHC(PPh3)CH}Cl2(PPh3)2]Cl with DPPM produced osmabenzenes [Os{CHC(PPh3)CHC(PPh3)CH}Cl2{(PPh2)CH2(PPh2)}]Cl ( 2 ), [Os{CHC(PPh3)CHC(PPh3)CH}Cl{(PPh2)CH2(PPh2)}2]Cl2 ( 3 ), and cyclic osmium η2‐allene complex [Os{CH?C(PPh3)CH?(η2‐C?CH)}Cl2{(PPh2)CH2(PPh2)}2]Cl ( 4 ). When the analogue complex of osmabenzene 1 , ruthenabenzene [Ru{CHC(PPh3)CHC(PPh3)CH}Cl2(PPh3)2]Cl, was used, the reaction produced ruthenacyclohexadiene [Ru{CH?C(PPh3)CH?C(PPh3)CH}Cl{(PPh2)CH2(PPh2)}2]Cl2 ( 6 ), which could be viewed as a Jackson–Meisenheimer complex. Complex 6 is unstable in solution and can easily be convert to the cyclic ruthenium η2‐allene complexes [Ru{CH?C(PPh3)CH?(η2‐C?CH)}Cl{(PPh2)CH2(PPh2)}2]Cl2 ( 7 ) and [Ru{CH?C(PPh3)CH?(η2‐C?CH)}Cl2{(PPh2)CH2(PPh2)}2]Cl ( 8 ). The key intermediates of the reactions have been isolated and fully characterized, further supporting the proposed mechanism for the reactions. Similar reactions also occurred in phosphonium‐substituted metallapyridinium [OsCl2{NHC(CH3)C(Ph)C(PPh3)CH}(PPh3)2]BF4 to give the cyclic osmium η2‐allene‐imine complex [OsCl2{NH?C(CH3)C(Ph)?(η2‐C?CH)}{(PPh2)CH2(PPh2)}(PPh3)]BF4 ( 11 ). 相似文献
14.
《Journal of organometallic chemistry》1987,329(2):209-215
The complexes [MI2(CO)3(NCMe)2] (M = Mo or W) react with one equivalent of L in CH2Cl2 at room temperature to give initially the mononuclear seven-coordinate complexes [MI2(CO)3(NCMe)L] which have been isolated for M = W; L = 3Cl-py, 3Br-py, 4Cl-py and 4Br-py. These compounds dimerise to give the iodidebridged dimers [M(μ-I)I(CO)3L]2 by displacement of acetonitrile. When M = Mo; L = 3Cl-py, 3Br-py, 4Cl-py and 4Br-py, and when M = Mo and W; L = py, 2Me-py (for M = W only), 4Me-py, 3,5-Me2-py, 2Cl-py and 2Br-py, only the dimeric complexes have been isolated. The ease of dimerisation of [MI2(CO)3(NCMe)L] is discussed in terms of the steric and electronic effects of the substituted pyridines. 相似文献
15.
Claire J Beddows Matthew R Box Christopher Butters Nicholas Carr Michael Green Monika Kursawe Mary F Mahon 《Journal of organometallic chemistry》1998,550(1-2)
Reaction of cis-[Mo(NCMe)2(CO)2(η5-L)][BF4] (L=C5H5 or C5Me5) with 1-acetoxybuta-1,3-diene gives the cationic complexes [Mo{η4-syn-s-cis-CH2CHCHCH(OAc)}(CO)2(η5-L)][BF4], which, on reaction with aqueous NaHCO3/CH2Cl2, afford good yields of the anti-aldehyde substituted complexes [Mo{η3-exo-anti-CH2CHCH(CHO)}(CO)2(η5-L)] 2 (L=C5Me5), 4 (L=C5H5)]. The corresponding η5-indenyl substituted complex 5 was prepared by protonation (HBF4·OEt2) of [Mo(η3-C3H5)(CO)2(η5-C9H7)] followed by addition of CH2=CHCH=CH(OAc) and hydrolysis (aq. NaHCO3/CH2Cl2). An X-ray crystallographic study of complex 2 confirmed the structure and showed that there is a contribution from a zwitterionic form involving donation of electron density from the molybdenum to the aldehyde carbonyl group. Treatment of 2 and 4, in methanol solution, with NaBH4 afforded the alcohols [Mo{η3-exo-anti-CH2CHCHCH2(OH)}(CO)2(η5-L)] [6 (L=C5H5), 8 (L=C5Me5)]; however, prolonged (30 h) reaction with NaBH4/MeOH surprisingly gave good yields of the methoxy-substituted complexes [Mo{η3-exo-anti-CH2CHCHCH2(OMe)}(CO)2(η5-L)] [7 (L=C5H5), 9 (L=C5Me5)], the structure of 7 being confirmed by single crystal X-ray crystallography. This methoxylation reaction can be explained by coordination of the hydroxyl group present in 6 and 8 onto B2H6 to form the potential leaving group HOBH3−, which on ionisation affords [Mo(η4-exo-buta-1-3-diene)(CO)2(η5-L)]+ which is captured by reaction with OMe−. Complex 8 is also formed in good yield on reaction of 2 with HBF4·OEt2 followed by treatment of the resulting cation [Mo{η4-exo-s-cis-syn-CH2CHCHCH(OH)}(CO)2(η5-C5Me5)][BF4] with Na[BH3CN]. Reaction of 4 with the Grignard reagents MeMgI, EtMgBr or PhMgCl afforded moderate yields of the alcohols [Mo{η3-exo-anti-CH2CHCHCH(OH)R}(CO)2(η5-C5H5)] [11 (R=Me), 12 (R=Et), 13 (R=Ph)]. Similarly, treatment of 2 with MeLi gave the corresponding alcohol 14. An attempt to carry out the Oppenauer oxidation [Al(OPr′)3/Me2CO] of 11 resulted in an elimination reaction and the formation of the η3-s-pentadienyl complex [Mo{η3-exo-anti-CH2CHCH(CHCH2)}(CO)2(η5-C5H5)], which was structurally identified by X-ray crystallography. Interestingly, oxidation of 6 with [Bu4nN][RuO4]/morpholine-N-oxide affords the aldehyde complex, 4 in good yield. Finally, reaction of 11 with [NO][BF4] followed by addition of Na2CO3 affords the fur-3-ene complex [Mo{η2-
(H)Me}(CO)(NO)(η5-C5H5)]. 相似文献
16.
Evans O. Changamu Holger B. Friedrich 《Journal of organometallic chemistry》2008,693(21-22):3351-3356
The halogenoalkyl complexes [Cp(CO)2M{(CH2)nX}] (n = 3–10, 12, M = Fe; n = 5, 6, M = Ru, X = Br, I) react with Ph3CPF6 in dry CH2Cl2 to give the corresponding carbocation complexes [Cp(CO)2M{η2-(CH2CH(CH2)n?2X}]PF6 in high yields. NMR evidence indicates that the metals form metallacyclopropane type structures with the carbocation ligand. The reactions of some of the cationic complexes with NaI, PPh3, Na[Cp(CO)2Fe] and Et3N are discussed. NaI and Na[Cp(CO)2Fe] displace the halogeno-olefin, while PPh3 adds at the β-CHδ+ giving the unstable phosphonium adducts [Cp(CO)2Fe{CH2CH(PPh3)(CH2)n?2X}]PF6 which decompose to the halogeno-olefins and the cationic PPh3 complex [Cp(CO)2Fe(PPh3)]+. Et3N causes allylic deprotonation forming internal olefin complexes of the type [Cp(CO)2Fe{CH2CHCH(CH2)n?3X}]PF6. 相似文献
17.
Luis Adrio Gemma Alberdi Adriana Amoedo Darío Lata Alberto Fernndez Javier Martínez M. Teresa Pereira Jos M. Vila 《无机化学与普通化学杂志》2005,631(11):2197-2203
Reaction of the thiosemicarbazone ligands C4H4NC(H)=NN(H)C(S)NHR (R = Me, a ; Et, b ) with Li2[PdCl4] gave the dinuclear complexes [Pd{C4H4NC(H)=NNC(S)NHR}(μ‐Cl)]2 (R = Me, 1a ; Et, 1b ) with a central Pd2Cl2 core and with deprotonation of the thiosemicarbazones at the hydrazinic nitrogen atom. Treatment of 1a and 1b with triphenylphosphine gave the mononuclear compounds [Pd{C4H4C(H)=NNC(S)NHR}(Cl)(PPh3)] (R = Me, 2a ; Et, 2b ), whereas reaction of 1a and 1b with tertiary diphosphines gave mono‐ and dinuclear compounds, as appropriate, with the corresponding diphosphine acting as a monodentate ( 6b ), chelating ( 3a ) and bridging ligand ( 4a, 5a , 4b, 5b ). Treatment of 1a and 1b with (Ph2PCH2CH2PPh2)W(CO)5 gave the new heterobimetallic complexes 7a and 7b . The crystal structures of complexes 3a and 4a are described. 相似文献
18.
Martínez-Salvador S Forniés J Martín A Menjón B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(29):8085-8097
The homoleptic, square‐planar organoplatinum(II) compound [NBu4]2[Pt(CF3)4] ( 1 ) undergoes oxidative addition of CF3I under mild conditions to give rise to the octahedral organoplatinum(IV) complex [NBu4]2[Pt(CF3)5I] ( 2 ). This highly trifluoromethylated species reacts with Ag+ salts of weakly coordinating anions in Me2CO under a wet‐air stream to afford the aquo derivative [NBu4][Pt(CF3)5(OH2)] ( 4 ) in around 75 % yield. When the reaction of 2 with the same Ag+ salts is carried out in MeCN, the solvento compound [NBu4][Pt(CF3)5(NCMe)] ( 5 ) is obtained in around 80 % yield. The aquo ligand in 4 as well as the MeCN ligand in 5 are labile and can be cleanly replaced by neutral and anionic ligands to furnish a series of pentakis(trifluoromethyl)platinate(IV) compounds with formulae [NBu4][Pt(CF3)5(L)] (L=CO ( 6 ), pyridine (py; 7 ), tetrahydrothiophene (tht; 8 )) and [NBu4]2[Pt(CF3)5X] (X=Cl ( 9 ), Br ( 10 )). The unusual carbonyl–platinum(IV) derivative [NBu4][Pt(CF3)5(CO)] ( 6 ) is thermally stable and has a νCO of 2194 cm?1. The crystal structures of 2? CH2Cl2, 5 , [PPh4][Pt(CF3)5(CO)] ( 6′ ), and 7 have been established by X‐ray diffraction methods. Compound 2 has shown itself to be a convenient entry to the chemistry of highly trifluoromethylated platinum compounds. To the best of our knowledge, compounds 2 and 4 – 10 are the organoelement compounds with the highest CF3 content to have been isolated and adequately characterized to date. 相似文献
19.
Summary
Trans-[RhCl(CO)L2] (L = PPh3, AsPh3 or PCy3) react with AgBF4 in CH2Cl2 to give the novel species [Rh-(CO)L2]+ [BF4]–.nCH2Cl2 (n = 1/2 or 1 1/2) (1–3), which we believe to be stabilised by weak solvent interaction. The corresponding stibine compound cannot be isolated by the same process, instead [Rh(CO)2(SbPh3)3]+ [BF4]– (7) is formed when the reaction is carried out in the presence of CO. When reactions designed to prepare [Rh(CO)L2]+ [BF4]– are performed in the presence of CO, or [Rh(CO)L2]+ [BF4]– complexes are reacted with CO, [Rh(CO)2L2]+ [BF4]– (L = PPh3, AsPh3 or PCy3) (4–6) are formed. If Me2CO is used as solvent in the preparation of [Rh(CO)L2]+ [BF4]– (L = PPh3 or AsPh3), then the products are the four-coordinate [Rh(CO)L2-(Me2CO)]+ [BF4]– (8,9) species. The complexes have been characterised by i.r., 31P and 1H n.m.r. spectroscopy and elemental analyses. 相似文献
20.
Paul K. Baker Lesley L. Howells Stuart G. Fraser Gordon W. Rogers Martin J. Snowden 《Transition Metal Chemistry》1990,15(1):71-74
Summary The seven-coordinate complexes [MI2(CO)3(NCMe)2] (M=Mo or W) react with two equivalents of L(L=py, 4Me-py, 3Cl-py or 3Br-py) or one equivalent of NN {NN=2,2-bipyridine(bipy), 1,10-phenanthroline(phen), 5,6-dimethyl-1, 10-phenanthroline (5,6-Me2-1, 10-phen), 5-Nitro-1, 10-phenanthroline (5-NO2-1, 10-phen) and C6H4(o-NH2)2 (o-diam) (for M=Mo only)} in CH2Cl2 at room temperature to give the substituted products [MI2(CO)3L2] or [MI2(CO)3(NN)] (1–17) in high yield. The compounds [MI2(CO)3(NCMe)2] react with two equivalents of NN (for M=W, NN=bipy; for M=Mo, NN=phen) to give the dicationic salts [M(CO)3(NN)2]2I(18–19). The compounds [MI2(CO)3(NCMe)2] (M=Mo or W) react with two equivalents of 5,6-Me2-1, 10-phen to yield the monocationic dicarbonyl compounds [MI(CO)2(5,6-Me2-phen)2]I (20 and21). The dicationic mixed ligand complexes [M(CO)3(bipy)(5,6-Me2-phen)]2I (22 and23) are prepared by reacting [MI2(CO)3(NCMe)2] with one equivalent of bipy, followed by anin situ reaction with 5,6-Me2-1, 10-phen to afford the products22 and23. The complexes (1–23) described in this paper have been characterised by elemental analysis (C, H and N), i.r. spectroscopy and, in selected cases,1Hn.m.r. spectroscopy. Magnetic susceptibility measurements show the compounds to be diamagnetic. 相似文献