共查询到20条相似文献,搜索用时 15 毫秒
1.
Gerard de Leeuw John S. Field Raymond J. Haines Beth McCulloch Elsie Meintjies Christiaan Monberg Gillian M. Olivier Praveen Ramdial Clifford N. Sampson Beate Sigwarth Nick D. Steen Kandasamy G. Moodley 《Journal of organometallic chemistry》1984,275(1):99-111
Reaction of [Fe2(CO)9] with a half molar amount of R2PYPR2 (Y = CH2, R = Ph, Me, OMe or OPri; Y = N(Et), R = OPh, OMe or OCH2; Y = N(Me), R = OPri or OEt) leads to the ready formation of a product which on irradiation with ultraviolet light rapidly decarbonylates to the heptacarbonyl derivative [Fe2(μ-CO)(CO)6{μ-R2PYPR2}]. Treatment of the latter with a slight excess of the appropriate ligand results, under photochemical conditions, in the formation of the dinuclear pentacarbonyl complex [Fe2(μ-CO)(C))4{μ-R2PYPR2}2] but under thermal conditions in the formation of the mononuclear species [Fe(CO)3{R2PYPR2}]. Reaction of [Ru3(CO)12] with an equimolar amount of (RO)2PN(R′)P(OR)2 (R′ = Me, R = Pri or Et; R′ = Et, R = Ph or Me) under either thermal or photochemical conditions produces [Ru3(CO)10{μ-(RO)2PN(OR)2}] which reacts further with excess (RO)2PN(R′)P(OR)2 on irradiation with ultraviolet light to afford the dinuclear compound [Ru2(μ-CO)(CO4{μ-(RO)2PN(R′)P(OR)2}2]. The molecular structure of [Ru2(μ-CO)(CO)4{μ-(MeO)2PN(Et)P(OMe)2}2], which has been determined by X-ray crystallography, is described. 相似文献
2.
Timothy R. Totsch Victoria L. Stanford Oleksander Klep Mary K. Burdette Benjamin Grant Stephen H. Foulger Gary M. Gray 《Journal of polymer science. Part A, Polymer chemistry》2020,58(13):1825-1842
Linear polyphosphonates with the generic formula –[P(Ph)(X)OR′O]n– (X = S or Se) have been synthesized by polycondensations of P(Ph)(NEt2)2 and a diol (HOR′OH = 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, tetraethylene glycol, or 1,12-dodecanediol) followed by reaction with a chalcogen. Random copolymers have been synthesized by polycondensations of P(Ph)(NEt2)2 and mixture of two of the diols in a 2:1:1 mol ratio followed by reaction with a chalcogen. Block copolymers with the generic formula –[P(Ph)(X)OR′O](x + 2) –[P(Ph)(X)OR′O](x + 3)– (X = S or Se) have been synthesized by the polycondensations of Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2 oligomers with HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers followed by reaction with a chalcogen. The Et2N[P(Ph)(X)OR′O](x + 2)P(Ph)NEt2 oligomers are prepared by the reaction of an excess of P(Ph)(NEt2)2 with a diol while the HOR′O[P(Ph)(X)OR′O](x + 3)H oligomers are prepared by the reaction of P(Ph)(NEt2)2 with an excess of the diol. In each case the excess, x is the same and determines the average block sizes. All of the polymers were characterized using 1H, 13C{1H}, and 31P{1H} NMR spectroscopy, TGA, DSC, and SEC. 31P{1H} NMR spectroscopy demonstrates that the random and block copolymers have the expected arrangements of monomers and, in the case of block copolymers, verifies the block sizes. All polymers are thermally stable up to ~300°C, and the arrangements of monomers in the copolymers (block vs. random) affect their degradation temperatures and Tg profiles. The polymers have weight average MWs of up to 3.8 × 104 Da. 相似文献
3.
《Journal of organometallic chemistry》2003,665(1-2):226-232
Photolysis of a benzene solution containing [Fe3(CO)9(μ3-E)2] (E=S, Se), [(η5-C5R5)Fe(CO)2(CCRI)] (R=H, Me; RI=Ph, Fc), H2O and Et3N results in formation of new metal clusters [(η5-C5R5)Fe3(CO)6(μ3-E)(μ3-ECCH2RI)] (R=H, RI=Ph, E=S 1 or Se 2; R=Me, RI=Ph, E=S 3 or Se 4; R=H, RI=Fc, E=S 5; R=Me, RI=Fc, E=S 6 or Se 7). Reaction of [Fe3(CO)9(μ3-S)2]with [(η5-C5R5)Mo(CO)3(CCPh)] (R=H, Me), under same conditions, produces mixed-metal clusters [(η5-C5R5)MoFe2(CO)6(μ3-S)(μ-SCCH2Ph)] (R=H 8; R=Me 9). Compounds 1–9 have been characterised by IR and 1H and 13C-NMR spectroscopy. Structures of 1, 5 and 9 have been established crystallographically. A common feature in all these products is the formation of new C-chalcogen bond to give rise to a (ECCH2RI) ligand. 相似文献
4.
Véronique Plantevin 《Journal of organometallic chemistry》2004,689(11):2013-2024
Further investigations into the chemistry of the rhenacyclobutadiene complexes (CO)4Re(η2-C(R)C(CO2Me)C(X)) (1: R=Me, X=OEt (1a), O(CH2)3CCH (1b), NEt2 (1c); R=CHEt2, X=OEt (1d); R=Ph, X=OEt (1e)) are reported. Reactions of 1 with alkynes at reflux temperature of toluene and at ambient temperature either under photochemical conditions or in the presence of PdO yield ring-substituted η5-cyclopentadienylrhenium tricarbonyl complexes, 2. The symmetrical alkynes R′CCR′ (R′=Ph, Me, CO2Me) afford the pentasubstituted complexes (η5-C5(Me)(CO2Me)(OEt)(Ph)(Ph))Re(CO)3 (2d), (η5-C5(Me)(CO2Me)(OEt)(Me)(Me))Re(CO)3 (2e), (η5-C5(Me)(CO2Me)(OEt)(CO2Me)(CO2Me))Re(CO)3 (2f), and (η5-C5(Me)(CO2Me)(NEt2)(CO2Me)(CO2Me))Re(CO)3 (2i) on reaction with the appropriate 1, whereas the unsymmetrical alkynes R′CCR″ (R′=Ph; R″=H, Me) give either only one, (η5-C5(Me)(CO2Me)(OEt)(Ph)H)Re(CO)3 (2a)), or both, (η5-C5(Me)(CO2Me) (OEt)(Ph)(Me))Re(CO)3 (2b) and (η5-C5(Me)(CO2Me)(OEt)(Me)(Ph))Re(CO)3 (2c), (η5-C5(Ph)(CO2Me)(OEt)(Ph)H)Re(CO)3 (2g) and (η5-C5(Ph)(CO2Me)(OEt)(H)(Ph))Re(CO)3 (2h), of the possible products of [3 + 2] cycloaddition of alkyne to η2-C(R)C(CO2Me)C(X). Thermolysis of (CO)4Re(η2-C(Me)C(CO2Me)C(O(CH2)3CCH)) (1b) containing a pendant alkynyl group proceeds to (η5-C5(Me)(CO2Me)(O(CH2)3)H)Re(CO)3 (2j), a η5-cyclopentadienyl-dihydropyran fused-ring product. Competition experiments showed that each of PhCCH and MeO2CCCCO2Me reacts faster than PhCCPh with 1a. The results with unsymmetrical alkynes are rationalized by steric properties of substituents at the CC and ReC bonds and by a preference of ReC(Me) over ReC(OEt) to undergo alkyne insertion. A mechanism is proposed that involves substitution of a trans CO by alkyne in 1, insertion of alkyne into ReC bond to give a rhenabenzene intermediate, and collapse of the latter to 2. Complexes 1a and 1d undergo rearrangement in MeCN at reflux temperature to give rhenafuran-like products, (CO)4Re(κ2-OC(OMe)C(CHCR2)C(OEt)) (R=H (3a) or Et (3b)). The reaction of 1d also proceeds in EtCN, PhCN, and t-BuCN at comparable temperature, but is slower (especially in t-BuCN) than in MeCN. In pyridine at reflux temperature, 1a undergoes a similar rearrangement, with CO substitution, to give (CO)3(py)Re(κ2-OC(OMe)C(CHCEt2)C(OEt)) (4). A mechanism is proposed for these reactions. The sulfonium ylides Me2SCHC(O)Ph and Me2SC(CN)2 (Me2SCRR′) react with 1a in acetonitrile at reflux temperature by nucleophilic addition of the ylide to the ReC(Me) carbon, loss of Me2S, and rearrangement to a rhenafuran-type structure to yield (CO)4Re(κ2-OC(OMe)C(C(Me)CRR′)C(OEt)) (R=H, R′=C(O)Ph (5a); R=R′CN (5b)). All new compounds were characterized by a combination of elemental analysis, mass spectrometry, and IR and NMR spectroscopy. 相似文献
5.
Photolysis of t-BuHgCl/KI with PhC(R2)C(R1)NO2 forms PhC(R2)C(R1)Bu-t when R1 = R2 = H or in low yield when R1 = H, R2 = Ph. When R1 ≠ H, or when R2 = Ph, reactions with t-BuHgI/KI/hv proceed mainly via PhC(R2)C(R1)NO2·-, PhC(R2)C(R1)N(OBu-t)O−HgX+, PhC(R2)C(R1)NO and PhC(R2)C(R1)N(OBu-t)HgX to form a variety of novel products including the dimeric bisnitronic esters ( 6 ) with R1 = Me or Ph and R2 = H; PhCH(R2)C(R1) = NOBu-t with R1 = Me or Ph and R2 = H or R1 = H and R2 = Ph; PhC(R2)(OBu-t)C(R1)NOH with R1 = H or Me and R2 = Ph; and 3-phenyl-2-R1-indoles with R1 = H, Me, Ph, PhS or t-BuS and R2 = Ph. Nitrosoaromatics react with t-BuHgX in the dark to form ArN(OBu-t)(OBu-t)HgX+ which condenses with ArNO to form the azoxy compound. tert-Butyl radicals will add to RNO2 [R = Ph, Ph2CCH, Ph2CC(Ph)] in the presence of t-BuHgI2− to form products derived from RN(OBu-t)O−HgI+. 相似文献
6.
Summary Rhodium(I), iridium(I), palladium(II) and platinum(II) complexes of the phosphinoamide ligands, Ph2PCH2CONHR (R = H, HDPA; Me, MDPA; Ph, PDPA) were prepared and characterized by using conductivity data, i.r., 1H and 31P(H) n.m.r. spectral data. Reaction of the ligands with MCl(PPh3)3 and MCl(CO)(PPh3)2 (M = Rh, Ir) in CH2Cl2 under reflux lead to the formation of MCl(PPh3)2 [Ph2PCH2C(O)NHR] and MCl(CO)(PPh3)[Ph2PCH2–C(O)HNR] respectively. The reaction of either K2MCl4 or cis-MCl2(PPh3)2 affords complexes of the type cis-MCl2[Ph2PCH2C(O)NHR]2 (M = Pd, Pt). A similar product results even from the reaction of phosphinoamides with cis-platin. Possible structures are proposed for the complexes based on their physicochemical data 相似文献
7.
《Journal of organometallic chemistry》1986,310(2):C42-C46
Dissolution of [Fe2(μ-CO)(CO)4{μ-(RO)2PN(Et)P(OR)2}2] (R = Me, Pri or Ph) and [Ru2(μ-CO)(CO)4{μ-(RO)2PN(Et)P(OR)2}2](R = Me or Pri) in CCl4 leads to the rapid formation of [Fe2(μ-Cl)(CO)4 {μ-(RO)2PN(Et)P(OR)2}2]Cl and [Ru2Cl2(CO)4 {μ-(RO)2 PN(Et)P(OR)2}2], respectively, with the latter isomerising in dichloromethane or chloroform solution to [Ru2(μ-Cl)(Cl(CO)4{μ-(RO)2PN(Et)P(OR)2}2]Cl, which in turn decarbonylates to [Ru2(μ-Cl)Cl(CO)3{μ-(RO)2PN(Et)P(OR)2}2]; the structure of [Ru2Cl2(CO)4{μ-(MeO)2PN(Et)P(OMe)2}2] has been established X-ray crystallographically. 相似文献
8.
Rufen Zhang Zhengsong Hu Qianli Li Peizhen Yan Suna Wang Chunlin Ma 《Heteroatom Chemistry》2014,25(4):217-225
Six new arenetelluronic triorganotin esters, namely (R3Sn)4[ArTe(μ‐O)(OH)O2)]2 (Ar = Ph, R = Me: 1 , R = Ph: 2 ; Ar = 3‐Me‐Ph, R = Me: 3 , R = Ph: 4 , Ar = 3‐Cl‐Ph, R = Me: 5 , R = Ph: 6 ), were prepared by treating arenetelluronic acids with the corresponding R3SnCl (R = Me, Ph) with potassium hydroxide in methanol. All complexes were characterized by elemental analysis, FT‐IR, NMR (1H, 13C, 119Sn) spectroscopy, and X‐ray crystallography. The structural analyses indicate that these complexes are isostructural as Sn4Te2 moiety, in which the Te2(μ2‐O)2 units are situated in the center and each Te atom is coordinated with two OSnR3 groups on the side. Complexes 1 , 3 , and 5 show one‐dimensional chain and two‐dimensional network supramolecular structures by intermolecular C H···O or C H···Cl interactions. The antitumor activities of these complexes reveal that most arenetelluronic triorganotin esters have powerful antitumor activities with certain regularity. 相似文献
9.
Georg Grötsch Wolfgang Malisch Herbert Blau 《Journal of organometallic chemistry》1983,252(2):C19-C22
The reaction of the phosphonium metallates Me4P[C5R5(CO)(Me3P))R′] (M = W, R = H, R′ = Et (1a); M = Mo, R = Me, R′ = Me (1b)) with the silylating reagent Me3SiOSO2CF3 yields the neutral complexes C5R5(CO)(Me3P))R (2a, 2b) bearing a chelating O(2), C(4)-trimethylsiloxybutenone ligand. The structure of the new compounds is established by the IR, 1H and 31P NMR spectra. 相似文献
10.
Sondes Lounissi Dr. Giuseppe Zampella Dr. Jean‐François Capon Prof. Luca De Gioia Prof. Fatma Matoussi Sélim Mahfoudhi Prof. François Y. Pétillon Prof. Philippe Schollhammer Dr. Jean Talarmin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(35):11123-11138
The behavior of [Fe2(CO)4(κ2‐PNPR)(μ‐pdt)] (PNPR=(Ph2PCH2)2NR, R=Me ( 1 ), Ph ( 2 ); pdt=S(CH2)3S) in the presence of acids is investigated experimentally and theoretically (using density functional theory) in order to determine the mechanisms of the proton reduction steps supported by these complexes, and to assess the role of the PNPR appended base in these processes for different redox states of the metal centers. The nature of the R substituent of the nitrogen base does not substantially affect the course of the protonation of the neutral complex by CF3SO3H or CH3SO3H; the cation with a bridging hydride ligand, 1 μH+ (R=Me) or 2 μH+ (R=Ph) is obtained rapidly. Only 1 μH+ can be protonated at the nitrogen atom of the PNP chelate by HBF4?Et2O or CF3SO3H, which results in a positive shift of the proton reduction by approximately 0.15 V. The theoretical study demonstrates that in this process, dihydrogen can be released from a η2‐H2 species in the FeIFeII state. When R=Ph, the bridging hydride cation 2 μH+ cannot be protonated at the amine function by HBF4?Et2O or CF3SO3H, and protonation at the N atom of the one‐electron reduced analogue is also less favored than that of a S atom of the partially de‐coordinated dithiolate bridge. In this situation, proton reduction occurs at the potential of the bridging hydride cation, 2 μH+ . The rate constants of the overall proton reduction processes are small for both complexes 1 and 2 (kobs≈4–7 s?1) because of the slow intramolecular proton migration and H2 release steps identified by the theoretical study. 相似文献
11.
Dr. Carina Vidovič Prof. Dr. Ferdinand Belaj Prof. Dr. Nadia C. Mösch-Zanetti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(54):12431-12444
A series of WIV alkyne complexes with the sulfur-rich ligand hydridotris(2-mercapto-1-methylimidazolyl) borate) (TmMe) are presented as bio-inspired models to elucidate the mechanism of the tungstoenzyme acetylene hydratase (AH). The mono- and/or bis-alkyne precursors were reacted with NaTmMe and the resulting complexes [W(CO)(C2R2)(TmMe)Br] (R=H 1 , Me 2 ) oxidized to the target [WE(C2R2)(TmMe)Br] (E=O, R=H 4 , Me 5 ; E=S, R=H 6 , Me 7 ) using pyridine-N-oxide and methylthiirane. Halide abstraction with TlOTf in MeCN gave the cationic complexes [WE(C2R2)(MeCN)(TmMe)](OTf) (E=CO, R=H 10 , Me 11 ; E=O, R=H 12 , Me 13 ; E=S, R=H 14 , Me 15 ). Without MeCN, dinuclear complexes [W2O(μ-O)(C2Me2)2(TmMe)2](OTf)2 ( 8 ) and [W2(μ-S)2(C2Me2)(TmMe)2](OTf)2 ( 9 ) could be isolated showing distinct differences between the oxido and sulfido system with the latter exhibiting only one molecule of C2Me2. This provides evidence that a fine balance of the softness at W is important for acetylene coordination. Upon dissolving complex 8 in acetonitrile complex 13 is reconstituted in contrast to 9 . All complexes exhibit the desired stability toward water and the observed effective coordination of the scorpionate ligand avoids decomposition to disulfide, an often-occurring reaction in sulfur ligand chemistry. Hence, the data presented here point toward a mechanism with a direct coordination of acetylene in the active site and provide the basis for further model chemistry for acetylene hydratase. 相似文献
12.
Marino Basato Prof. Cristina Tubaro Dr. Andrea Biffis Dr. Marco Bonato Dr. Gabriella Buscemi Dr. Filippo Lighezzolo Dr. Pamela Lunardi Dr. Chiara Vianini Dr. Franco Benetollo Dr. Alessandro Del Zotto Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(6):1516-1526
The reaction of diazo compounds with alkenes catalysed by complex [RuCl(cod)(Cp)] (cod=1,5‐cyclooctadiene, Cp=cyclopentadienyl) has been studied. The catalytic cycle involves in the first step the decomposition of the diazo derivative to afford the reactive [RuCl(Cp){?C(R1)R2}] intermediate and a mechanism is proposed for this step based on a kinetic study of the simple coupling reaction of ethyl diazoacetate. The evolution of the Ru–carbene intermediate in the presence of alkenes depends on the nature of the substituents at both the diazo N2?C(R1)R2 (R1, R2=Ph, H; Ph, CO2Me; Ph, Ph; C(R1)R2=fluorene) and the olefin substrates R3(H)C?C(H)R4 (R3, R4=CO2Et, CO2Et; Ph, Ph; Ph, Me; Ph, H; Me, Br; Me, CN; Ph, CN; H, CN; CN, CN). A remarkable reactivity of the complex was recorded, especially towards unstable aryldiazo compounds and electron‐poor olefins. The results obtained indicate that either cyclopropanation or metathesis products can be formed: the first products are favoured by the presence of a cyano substituent at the double bond and the second ones by a phenyl. 相似文献
13.
Ludwig Maier 《Helvetica chimica acta》1969,52(3):827-845
High yields of bis-(dialkoxyphosphonyl-methyl)- phosphinic esters, (RO)2 (O)-PCH2P(O)OR, bis-(aloxyphosphinyl-methyl)-phosphinic esters, [R(RO)(O)PCH2]2P(O)OR, are obtained by heating bis-chloromethyl-phosphinic esters, (CICH2)2P(O)OR, with alkylphoshites, phosphonites and phosphinites, repectively, at 170 to 180°C for several hours. Hydrolysis of these esters in achieved by refluxing with conc. HCl for extended periods. Bis-(dihydroxyphosphonyl-methyl)-phosphinic acid, HO(O)P[CH2P(O) (OH)2]2, obtained by hydrolysis of the all-ethyl ester, titrates in aqueous solution as a tetrabasic acid with breaks at pH = 5,2 (three equivalents) and at pH = 8,8 (one equivalent). The fifth proton can be titrated only after addition of NaCl. This acid is an excellent chelating agent for metal ions. The 1H- and 31P-NMR. spectra of all the compounds prepared are discussed. 相似文献
14.
Functionally substituted triorganotin halides V–IX of type R2Sn(X)(CH2)2P(O)PhR′ (R = Me, t-Bu; Rt? = OEt, t-Bu; X = Cl, Br) have been synthesized by halogen cleavage of the corresponding tetraorganotin compounds R2R2Sn(CH2)2P(O)PhR′ (R2 = Me or Ph), I–IV. The solid state structure of Me2Sn (Br) (CH2)2P(O)PhBu-t (IX), determined by X-ray diffraction, shows a distorted trigonal-bipyramidal structure at the tin atom, with intramolecular coordination of the PO group. Spectroscopic data are in agreement with such a structure in solution for compounds V–IX. Upon varying the temperature, concentration or solvent in solutions of compounds V–IX a stereoisomerization is observed. On the basis of NMR 1H, 13C, 31P, 119Sn), IR and conductivity studies, it is suggested that this stereoisomerization involves a hexacoordinated transition state at the tin atom. 相似文献
15.
Preparation and Oxidative Derivatisation of Phosphonothionic Esters The kind of the amine used influences decisively course and rate of the reaction of trialkyl phosphites, (RO)3P (R = Me, Et, Ph) with H2S in the presence of different amines (Et3N, Et2NH, Et2NPh, pyridine). Phosphonothionic esters, (RO)2P(S)H (R = Me, Et, Bu), are obtained in over 80% yield by using pyridine as base and an alkali alcoholate as catalyst. The oxidative derivatisation of phosphonothionic esters by means of CCI4 and protic (4-nitrophenol, 2,4,5-trichlorophenol, ammonia, piperidine, phenylhydrazine) or anionic nucleophiles (F?, NCS?, NCO?, CN?, N3?) (Atherton-Todd reaction) yields thiophosphoric acid derivatives (RO)2P(S)Nuc (R = Me, Et, Bu: Nuc = 4-nitrophenoxy, PhNHNH; R = Me, Et: Nuc = 2,4,5-trichlorophenoxy, F, NCS, N3; R = Me: NH2, C5H10N; R = Et: Nuc = CI, CN) and in some cases the dealkylated products (RO)P(Nuc)SO? (R = Me; Nuc = CI, F, NCS, CN). The phosphazenes (EtO)2P(S)? N = PPh3 and (MeO)2P(S)? N ? P(OEt)3, up to now unknown in literature, were obtained by treating thiophosphoryl azides with PPh3 or P(OEt)3, resp. 相似文献
16.
Synthesis of Carboxylate Substituted Rhenium Gold Metallatetrahedranes Re2(AuPPh3)2(μ-PCy2)(CO)7(η1-OC(R)O) (R = H, Me, CF3, Ph, 3,4-(OMe)2C6H3) The reaction of the in situ prepared salt Li[Re2(μ-H)(μ-PCy2)(CO)7(ax-C(Ph)O)] ( 2 ) with 1,5 equivalents of monocarboxylic acid RCOOH (R = H ( 4 a ), Me ( 4 b ), CF3 ( 4 c ), Ph ( 4 d ), 3,4-(OMe)2C6H3 ( 4 e ) in tetrahydrofruan (THF) solution at 60 °C gives within 4 h under release of benzaldehyde (PhCHO) the η1-carboxylate substituted dirhenium salt Li[Re2(μ-H)(μ-PCy2)(CO)7(η1-OC(R)O)] (R = H ( 4 a ), Me ( 4 b ), CF3 ( 4 c ), Ph ( 4 d ), 3,4-(OMe)2C6H3 ( 4 e )) in almost quantitative yield. The lower the pKa value of the respective carboxylic acid the faster the reaction proceeds. It was only in the case of CF3COOH possible to prove the formation of the hydroxycarbene complex Re2(μ-H)(μ-PCy2)(CO)7(=C(Ph)OH) ( 5 ) prior to elimination of PhCHO. The new compounds 4 a–4 e were only characterized by 31P NMR and ν(CO) IR spectroscopy as they are only stable in solution. They are converted with two equivalents of BF4AuPPh3 at 0 °C in a so-called cluster expansion reaction into the heterometallic metallatetrahedrane complexes Re2(AuPPh3)2(μ-PCy2)(CO)7(η1-OC(R)O) (R = H ( 7 a ), Me ( 7 b ), CF3 ( 7 c ), Ph ( 7 d ), 3,4-(OMe)2C6H3 ( 7 e )) (yield 47–71% ). The expected precursor complexes of 7 a–7 e Li[Re2(AuPPh3)(μ-PCy2)(CO)7(η1-OC(R)O] ( 8 ) were not detected by NMR and IR spectroscopy in the course of the reaction. Their existence was retrosynthetically proved by the reaction of 7 b with an excess of the chelating base TBD (1,5,7-Triazabicyclo[4.4.0]dec-5-en) forming [(TBD)xAuPPh3][Re2(AuPPh3)(μ-PCy2)(CO)7(η1-OC(Me)O] ( 8 b ) in solution. The η1-bound carboxylate ligand in 7 a–7 e can photochemically be converted into a μ-bound ligand in Re2(AuPPh3)2(μ-PCy2)(μ-OC(R)O)(CO)6 (R = H ( 9 a ), Me ( 9 b ), CF3 ( 9 c ), Ph ( 9 d ), 3.4-(MeO)2C6H3 ( 9 e )) under release of one equivalent CO. All isolated cluster complexes were characterized and identified by the following analytical methods: elementary analysis, NMR (1H, 31P) spectroscopy, ν(CO) IR spectroscopy and in the case of 7 d and 9 b by X-ray structure analysis. 相似文献
17.
《Journal of organometallic chemistry》1987,322(1):C7-C12
Protonation of the dinuclear compounds [M2(μ-CO)(CO)4(μ-R2PYPR2)2] by HBF4 or HPF6 leads to the formation of crystalline cationic hydrido products [M2H(CO)5(μ-R2PYPR2)2]X and [M2(μ-H)(μ-CO)(CO)4(μ-R2PYPR2)2]X (X = BF4 or PF6) in which the hydride ligand is terminal for M = Ru, Y = N(Et) and R = OMe or OPri and bridging for M = Fe, Y = CH2 and R = Me or Ph, for M = Fe, Y = N(Et) and R = OMe, OEt, OPri or OPh and for M = Ru, Y = CH2 and R = Ph; the fluxional behaviour of [Ru2H(CO)5{μ-(RO)2PN(Et)P(OR)2}2]+ (R = Me or Pri) in solution is described. 相似文献
18.
Cadierno V Díez J García-Alvarez J Gimeno J Nebra N Rubio-García J 《Dalton transactions (Cambridge, England : 2003)》2006,(47):5593-5604
Reactions of [PdCl2(COD)] with 1 equiv. of the iminophosphorane-phosphine ligands Ph2PCH2P{=NP(=O)(OR)2}Ph2 (R=Et, Ph) lead to the novel Pd(II) derivatives cis-[PdCl2(kappa2-(P,N)-Ph2PCH2P{=NP(=O)(OR)2}Ph2)] (R=Et, Ph). Pd-N bond cleavage readily takes place upon treatment of these species with a variety of two-electron donor ligands. By this way, complexes cis-[PdCl2(kappa1-(P)-Ph2PCH2P{=NP(=O)(OR)2}Ph2)(L)] (R=Et, L=CNtBu, CN-2,6-C6H3Me2, py, P(OMe)3, P(OEt)3; R=Ph, L=CNtBu, CN-2,6-C6H3Me2, py, P(OMe)3, P(OEt)3) have been synthesized in high yields. The addition of two equivalents of ligands to dichloromethane solutions of [PdCl2(COD)] results in the formation of complexes trans-[PdCl2(kappa1-(P)-Ph2PCH2P{=NP(=O)(OR)2}Ph2)2] (R=Et, Ph), which can be converted into the dicationic species [Pd(Ph2PCH2P{=NP(=O)(OR)2}Ph2)2][SbF6]2 (R=Et, Ph) by treatment with AgSbF6. Complex also reacts with CNtBu to afford trans-[Pd(kappa1(P)-Ph2PCH2P{=NP(=O)(OPh)2}Ph2)2(CNtBu)2][SbF6]2. The structures of and have been determined by single-crystal X-ray diffraction methods. In addition, the ability of these Pd(II) complexes to promote the catalytic cycloisomerization of (Z)-3-methylpent-2-en-4-yn-1-ol into 2,3-dimethylfuran has also been studied. 相似文献
19.
Organotin(IV) carboxylates R2LNCSnOC(O)CH2P(E)Ph2, where LNC is an N‐chelating 2‐(dimethylamino)phenyl group, and R/E = Ph/void (1a), Ph/O (1b), Ph/S (1c), Me/void (2a), Me/O (2b) and Me/S (2c), were synthesized, characterized by 1H, 13C, 31P and 119Sn NMR, IR and MS spectra, and the solid‐state structures of 1b, 1c, 2b and 2c were determined by single‐crystal X‐ray diffraction. Spectral and structural data showed that the compounds are monomeric in CDCl3 solution and the solid state, with the organophosphorus groups in the α‐position of the monodentate carboxylate ligands not interacting with the tin atom. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
20.
Aroop K. Roy Urszula G. Wettermark Gary M. Scheide Patty Wisian-neilson Robert H. Neilson 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):147-153
Abstract The reactions of a variety of electrophiles with the N-silyl-P-trifluoroethoxyphosphoranimine anion Me3Sin°P(Me)(OCH2CF3)CH? 2 (1a), prepared by the deprotonation of the dimethyl precursor Me3SiN[dbnd]P(OCH2CF3)Me2 (1) with n-BuLi in Et2O at-78°C, were studied. Thus, treatment of 1a with alkyl halides, ethyl chloroformate, or bromine afforded the new N-silylphosphoranimine derivatives Me3SiN[dbnd]P(Me)(OCH2CF3)CH2R [2: R = Me, 3: R = CH2Ph, 4: R = CH[sbnd]CH2, 5: R = C(O)OEt, and 6: R = Br]. In another series, when 1a was allowed to react with various carbonyl compounds, 1,2-addition of the anion to the carbonyl group was observed. Quenching with Me3SiCl gave the O-silylated products Me3SiN[dbnd]P(Me)(OCH2CF3)CH2°C(OSiMe3)R1R2 [7: R 1 = R 2 = Me; 8: R 1 = Me, R 2 = Ph; 9: R1 = Me, R 2 = CH[sbnd]CH2; and 10: R 1 = H, R 2 = Ph]. Compounds 2–10 were obtained as distillable, thermally stable liquids and were characterized by NMR spectroscopy (1H, 13C, and 31P) and elemental analysis. 相似文献