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1.
Diimido, Imido Oxo, Dioxo, and Imido Alkylidene Halfsandwich Compounds via Selective Hydrolysis and α—H Abstraction in Molybdenum(VI) and Tungsten(VI) Organyl Complexes Organometal imides [(η5‐C5R5)M(NR′)2Ph] (M = Mo, W, R = H, Me, R′ = Mes, tBu) 4 — 8 can be prepared by reaction of halfsandwich complexes [(η5‐C5R5)M(NR′)2Cl] with phenyl lithium in good yields. Starting from phenyl complexes 4 — 8 as well as from previously described methyl compounds [(η5‐C5Me5)M(NtBu)2Me] (M = Mo, W), reactions with aqueous HCl lead to imido(oxo) methyl and phenyl complexes [(η5‐C5Me5)M(NtBu)(O)(R)] M = Mo, R = Me ( 9 ), Ph ( 10 ); M = W, R = Ph ( 11 ) and dioxo complexes [(η5‐C5Me5)M(O)2(CH3)] M = Mo ( 12 ), M = W ( 13 ). Hydrolysis of organometal imides with conservation of M‐C σ and π bonds is in fact an attractive synthetic alternative for the synthesis of organometal oxides with respect to known strategies based on the oxidative decarbonylation of low valent alkyl CO and NO complexes. In a similar manner, protolysis of [(η5‐C5H5)W(NtBu)2(CH3)] and [(η5‐C5Me5)Mo(NtBu)2(CH3)] by HCl gas leads to [(η5‐C5H5)W(NtBu)Cl2(CH3)] 14 und [(η5‐C5Me5)Mo(NtBu)Cl2(CH3)] 15 with conservation of the M‐C bonds. The inert character of the relatively non‐polar M‐C σ bonds with respect to protolysis offers a strategy for the synthesis of methyl chloro complexes not accessible by partial methylation of [(η5‐C5R5)M(NR′)Cl3] with MeLi. As pure substances only trimethyl compounds [(η5‐C5R5)M(NtBu)(CH3)3] 16 ‐ 18 , M = Mo, W, R = H, Me, are isolated. Imido(benzylidene) complexes [(η5‐C5Me5)M(NtBu)(CHPh)(CH2Ph)] M = Mo ( 19 ), W ( 20 ) are generated by alkylation of [(η5‐C5Me5)M(NtBu)Cl3] with PhCH2MgCl via α‐H abstraction. Based on nmr data a trend of decreasing donor capability of the ligands [NtBu]2— > [O]2— > [CHR]2— ? 2 [CH3]— > 2 [Cl]— emerges. 相似文献
2.
Rafael Fernández Dr. Abdessamad Grirrane Dr. Irene Resa Dr. Amor Rodríguez Dr. Ernesto Carmona Prof. Eleuterio Álvarez Dr. Enrique Gutiérrez‐Puebla Prof. Ángeles Monge Prof. Juan Miguel López del Amo Dr. Hans‐Heinrich Limbach Agustí Lledós Prof. Feliu Maseras Prof. Diego del Río Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(4):924-935
New zincocenes [ZnCp′2] ( 2 – 5 ) with substituted cyclopentadienyl ligands C5Me4H, C5Me4tBu, C5Me4SiMe2tBu and C5Me4SiMe3, respectively, have been prepared by the reaction of ZnCl2 with the appropriate Cp′‐transfer reagent. For a comparative structural study, the known [Zn(C5H4SiMe3)2] ( 1 ), has also been investigated, along with the mixed‐ring zincocenes [Zn(C5Me5)(C5Me4SiMe3)] ( 6 ) and [Zn(C5Me5)(C5H4SiMe3)] ( 7 ), the last two obtained by conproportionation of [Zn(C5Me5)2] with 5 or 1 , as appropriate. All new compounds were characterised by NMR spectroscopy, and by X‐ray methods, with the exception of 7 , which yields a side‐product ( C ) upon attempted crystallisation. Compounds 5 and 6 were also investigated by 13C CPMAS NMR spectroscopy. Zincocenes 1 and 2 have infinite chain structures with bridging Cp′ ligands, while 3 and 4 exhibit slipped‐sandwich geometries. Compounds 5 and 6 have rigid, η5/η1(σ) structures, in which the monohapto C5Me4SiMe3 ligand is bound to zinc through the silyl‐bearing carbon atom, forming a Zn? C bond of comparable strength to the Zn? Me bond in ZnMe2. Zincocene 5 has dynamic behaviour in solution, but a rigid η5/η1(σ) structure in the solid state, as revealed by 13C CPMAS NMR studies, whereas for 6 the different nature of the Cp′ ligands and of the ring substituents of the η1‐Cp′ group (Me and SiMe3) have permitted observation for the first time of the rigid η5/η1 solution structure. Iminoacyl compounds of composition [Zn(η5‐C5Me4R)(η1‐C(NXyl)C5Me4R)] resulting from the reactions of some of the above zincocenes and CNXyl (Xyl=2,6‐dimethylphenylisocyanide) have also been obtained and characterised. 相似文献
3.
A series of cycloalkylidene‐bridged mixed cyclopentadienyl‐indenyl tetracarbonyl diruthenium complexes (η5:η5‐RC5H3CR′2C9H6)Ru2(CO)2(µ‐CO)2 [R = H, R′, R′ = Me2 (1), (CH2)4 (2), (CH2)5 (3), (CH2)6 (4); R = tBu, R′, R′ = Me2 (5), (CH2)4 (6), (CH2)5 (7)] have been synthesized by reactions of the corresponding ligands RC5H4CR′2C9H7 with Ru3(CO)12 in refluxing xylene. The molecular structures of 2, 6 and 7 have been determined by X‐ray diffraction. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
4.
《应用有机金属化学》2017,31(8)
Treatment of Ru3(CO)12 with an equivalent of (2‐phenyl‐1H ‐inden‐3‐yl)dicyclohexylphosphine ( 1 ) and (2‐pyridyl‐1H ‐inden‐1‐yl)dicyclohexylphosphine ( 4 ) in refluxing heptane gave the novel trinuclear ruthenium clusters (μ3‐η1:η2:η5–2‐phenyl‐3‐Cy2PC9H4)Ru3(CO)8 ( 1c ) and [μ2‐η1–2‐(pyridin‐2‐yl)‐3‐Cy2PC9H6]Ru3(CO)9 ( 4a ), respectively, via C ─ H bond cleavage. (2‐Mesityl‐1H ‐inden‐3‐yl)dicyclohexylphosphine ( 2 ) reacted with Ru3(CO)12 in refluxing heptane to give the trinuclear ruthenium cluster [μ‐2‐mesityl‐(3‐Cy2PC9H5)](μ2‐CO)Ru3(CO)9 ( 2c ) via C ─ H bond cleavage and carbonyl insertion. 2‐(Anthracen‐9‐yl)‐1H –inden‐3‐yldicyclohexylphosphine ( 3 ) reacted with Ru3(CO)12 in refluxing heptane to give the dinuclear ruthenium cluster [μ2‐η3:η3–2‐(anthracen‐9‐yl)‐3‐Cy2PC9H6]Ru2(CO)5 ( 3a ). The structures of 1c , 2c , 3a and 4a were fully characterized using IR and NMR spectroscopy, elemental analysis and single‐crystal X‐ray diffraction. These results suggest that the 2‐aryl substituent on the indenyl ring has a pronounced effect on the reaction and coordination modes of Ru3(CO)12. 相似文献
5.
Zhiqiang Hao Ying Li Chen Li Ruitao Wu Zhihong Ma Suzhen Li Zhangang Han Xuezhong Zheng Jin Lin 《应用有机金属化学》2019,33(3)
Reactions of pyridine imines [C5H4N‐2‐C(H) = N‐C6H4‐R] [R = H (1), CH3 (2), OMe (3), CF3 (4), Cl (5), Br (6)] with Ru3(CO)12 in refluxing toluene gave the corresponding dinuclear ruthenium carbonyl complexes of the type {μ‐η2‐CH[(2‐C5H4N)(N‐C6H4‐R)]}2Ru2(CO)4(μ‐CO) [R = H (7); CH3 (8); OMe (9); CF3 (10); Cl (11); Br (12)]. All six novel complexes were separated by chromatography, and fully characterized by elemental analysis, IR, NMR spectroscopy. Molecular structures of 7, 10, 11, and 12 were determined by X‐ray crystal diffraction. Further, the catalytic performance of these complexes was also tested. The combination of {μ‐η2‐CH[(2‐C5H4N)(N‐C6H4‐R)]}2Ru2(CO)4(μ‐CO) and NMO afforded an efficient catalytic system for the oxidation of a variety secondary alcohols. 相似文献
6.
Ming Zhang Xiaoli Liu Chaojun Shi Chunxia Ren Yuqiang Ding Herbert W. Roesky 《无机化学与普通化学杂志》2008,634(10):1755-1758
Treatment of N‐heterocyclic silylene Si[N(tBu)CH]2 ( 1 ) and [(η3‐C3H5)PdCl]2 in toluene led to the formation of the mononuclear complex (η3‐C3H5)Pd{Si[N(tBu)CH]2}Cl ( 3 ), the silicon analogue to N‐heterocyclic carbene complex (η3‐C3H5)Pd{C[N(tBu)CH]2}Cl ( 2 ). Complex 3 was characterized with 1H NMR and 13C NMR. Investigation shows that (η3‐C3H5)Pd{Si[N(tBu)CH]2}Cl is an active catalyst for Heck coupling reaction of styrene with aryl bromides. 相似文献
7.
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XVII [1] [Co(g5‐Me5C5)(g3‐tBu2PPCH–CH3)] from [Co(g5‐Me5C5)(g2‐C2H4)2] and tBu2P–P=P(Me)tBu2 [Co(η5‐Me5C5)(η3‐tBu2PPCH–CH3)] 1 is formed in the reaction of [Co(η5‐Me5C5)(η2‐C2H4)2] 2 with tBu2P–P 4 (generated from tBu2P–P=P(Me)tBu2 3 ) by elimination of one C2H4 ligand and coupling of the phosphinophosphinidene with the second one. The structure of 1 is proven by 31P, 13C, 1H NMR spectra and the X‐ray structure analysis. Within the ligand tBu2P1P2C1H–CH3 in 1 , the angle P1–P2–C1 amounts to 90°. The Co, P1, P2, C1 atoms in 1 look like a „butterfly”︁. The reaction of 2 with a mixture of tBu2P–P=P(Me)tBu2 3 and tBu–C?P 5 yields [Co(η5‐Me5C5){η4‐(tBuCP)2}] 6 and 1 . While 6 is spontaneously formed, 1 appears only after complete consumption of 5 . 相似文献
8.
Syntheses, Structure and Reactivity of η3‐1,2‐Diphosphaallyl Complexes and [{(η5‐C5H5)(CO)2W–Co(CO)3}{μ‐AsCH(SiMe3)2}(μ‐CO)] Reaction of ClP=C(SiMe2iPr)2 ( 3 ) with Na[Mo(CO)3(η5‐C5H5)] afforded the phosphavinylidene complex [(η5‐C5H5)(CO)2Mo=P=C(SiMe2iPr)2] ( 4 ) which in situ was converted into the η1‐1,2‐diphosphaallyl complex [η5‐(C5H5)(CO)2Mo{η3‐tBuPPC(SiMe2iPr)2] ( 6 ) by treatment with the phosphaalkene tBuP=C(NMe2)2. The chloroarsanyl complexes [(η5‐C5H5)(CO)3M–As(Cl)CH(SiMe3)2] [where M = Mo ( 9 ); M = W ( 10 )] resulted from the reaction of Na[M(CO)3(η5‐C5H5)] (M = Mo, W) with Cl2AsCH(SiMe3)2. The tungsten derivative 10 and Na[Co(CO)4] underwent reaction to give the dinuclear μ‐arsinidene complex [(η5‐C5H5)(CO)2W–Co(CO)3{μ‐AsCH(SiMe3)2}(μ‐CO)] ( 11 ). Treatment of [(η5‐C5H5)(CO)2Mo{η3‐tBuPPC(SiMe3)2}] ( 1 ) with an equimolar amount of ethereal HBF4 gave rise to a 85/15 mixture of the saline complexes [(η5‐C5H5)(CO)2Mo{η2‐tBu(H)P–P(F)CH(SiMe3)2}]BF4 ( 18 ) and [Cp(CO)2Mo{F2PCH(SiMe3)2}(tBuPH2)]BF4 ( 19 ) by HF‐addition to the PC bond of the η3‐diphosphaallyl ligand and subsequent protonation ( 18 ) and/or scission of the PP bond by the acid ( 19 ). Consistently 19 was the sole product when 1 was allowed to react with an excess of ethereal HBF4. The products 6 , 9 , 10 , 11 , 18 and 19 were characterized by means of spectroscopy (IR, 1H‐, 13C{1H}‐, 31P{1H}‐NMR, MS). Moreover, the molecular structures of 6 , 11 and 18 were determined by X‐ray diffraction analysis. 相似文献
9.
1,2-Diphosphaferrocenes as Ligands in Transition Metal Complexes. X-Ray Structure Analysis of [(η5-1,3-tBu2C5H3){η5-1,2-[Co2(CO)6]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}] Reaction of metallo-1,2-diphosphapropene (η5-tBuC5H4)(CO)2Fe? P(SiMe3)? P?C(SiMe3)2 with (Z-cyclooctene)Cr(CO)5 afforded the pentacarbonylchromium adduct of a 1,2-diphosphaferrocene [(η5-tBuC5C5H4){η5-1-[Cr(CO)5]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] ( 1 c ). Diphosphaferrocene [(η5-tBuC5H4){η5-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] ( 2 c ) was formed when (η5-tBuC5H4)(CO)2FeBr was treated with (Me3Si)2P? P?C(SiMe3)2 in toluene at 60°C. Photolysis of molybdenum- and tungsten hexacarbonyl in the presence of [(η5-1,3-tBu2C5H3){η5-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] ( 2 b ) gave the pentacarbonylmetal adducts 8 (M = Mo) and 9 (M = W), respectively. A corresponding manganese derivative resulted from the photochemical reaction of 2 b and (MeC5H4)Mn(CO)3. Treatment of 2 b with Co2(CO)8 yielded trinuclear [(η5-1,3-tBu2C5H3){η5-1,2-[Co2(CO)6]-3,4-(Me3SiO)2-5-(Me3Si)P2C3}Fe] ( 11 ). Constitution and configuration of compounds 1 c, 2 c, 8 – 11 were determined by elemental analyses and spectra (IR, 1H-, 13C-, 31P-NMR, MS). In addition the molecular structure of 11 was established by single crystal X-ray analysis. 相似文献
10.
The reactions of PhCH2SiMe3 ( 1 ), PhCH2SiMe2tBu ( 2 ), PhCH2SiMe2Ph ( 3 ), 3,5‐Me2C6H3CH2SiMe3 ( 4 ), and 3,5‐Me2C6H3CH2SiMe2tBu ( 5 ) with nBuLi in tetramethylethylenediamine (tmeda) afford the corresponding lithium complexes [Li(tmeda)][CHRSiMe2R′] (R, R′ = Ph, Me ( 6 ), Ph, tBu ( 7 ), Ph, Ph ( 8 ), 3,5‐Me2C6H3, Me ( 9 ), and 3,5‐Me2C6H3, tBu ( 10 )), respectively. The new compounds 5 , 7 , 8 , 9 and 10 have been characterized by 1H and 13C NMR spectroscopy, compounds 7 , 8 and 9 also by X‐ray structure analysis. 相似文献
11.
Stable dinuclear transition metal complexes,[(η6‐C6H6)2Ru2(L1)Cl2]2+ ( 1 ), [(η6‐p‐iPrC6H4Me)2Ru2(L1)Cl2]2+ ( 2 ), [(η6‐C6Me6)2Ru2(L1)Cl2]2+ ( 3 ), [(η6‐C6H6)2Ru2(L2)Cl2]2+ ( 4 ),[(η6‐p‐iPrC6H4Me)2Ru2(L2)Cl2]2+ ( 5 ), [(η6‐C6Me6)2Ru2(L2)Cl2]2+ ( 6 ), [(η5‐C5Me5)2Rh2(L1)Cl2]2+ ( 7 ), [(η5‐C5Me5)2Ir2(L1)Cl2]2+ ( 8 ),[(η5‐C5Me5)2Rh2(L2)Cl2]2+ ( 9 ), and [(η5‐C5Me5)2Rh2(L2)Cl2]2+ ( 10 ), with the bis‐bidentate ligands 1,3‐bis(di‐2‐pyridylaminomethyl)benzene (L1) and 1,4‐bis(di‐2‐pyridylaminomethyl)benzene (L2), which contain two chelating dipyridylamine units connected by an aromatic spacer, were synthesized. The cationic dinuclear complexes were isolated as their hexafluorophosphate salts and characterized by using a combination of NMR, IR, and UV/Vis spectroscopic methods and mass spectrometry. The solid‐state structure of complex 8 as a representative was determined by X‐ray structure analysis. 相似文献
12.
Reaction of tert -Butyl-phosphaalkyne with Molybdenum Complexes The reaction of tBuC≡P with [(CH3CN)3Mo(CO)3] leads to the complex [Mo(CO)4〈Mo(CO)2(η4-P3CtBu){η4-P2(CtBu)2}〉] 1 as well as to the alkyne complexes [Mo(CO)4〈{P3(CtBu)2}{Mo(CO)2(CtBu)}{η3-P2(CtBu)2}〉] 2 and [Mo(CtBu){η4-P2(CtBu)2(CO)}{η5-P3(CtBu)2}] 3 . All compounds are characterized by X-ray structural analysis, by NMR- and IR spectroscopy and by mass spectrometry. In complex 1 a 1,3-diphosphacyclobutadiene and a 1,2,4-triphosphacyclobutadiene are connected by two molybdenum carbonyl centres. In 2 a 1,3-diphosphacyclobutadiene is π- and a novel 1,2,4-triphospholyl ligand is σ-bonded at two Mo centres. A characteristic feature of 3 besides a π co-ordinated 1,2,4-triphospholyl ligand is a 3,4-diphosphacyclopentadienone as ligand, formed via CO insertion during the cyclodimerisation of two phosphaalkynes. 相似文献
13.
Platinum Complexes of a Borane‐Appended Analogue of 1,1′‐Bis(diphenylphosphino)ferrocene: Flexible Borane Coordination Modes and in situ Vinylborane Formation
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Bradley E. Cowie Prof. David J. H. Emslie 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):16899-16912
A bis(phosphine)borane ambiphilic ligand, [Fe(η5‐C5H4PPh2)(η5‐C5H4PtBu{C6H4(BPh2)‐ortho})] (FcPPB), in which the borane occupies a terminal position, was prepared. Reaction of FcPPB with tris(norbornene)platinum(0) provided [Pt(FcPPB)] ( 1 ) in which the arylborane is η3BCC‐coordinated. Subsequent reaction with CO and CNXyl (Xyl=2,6‐dimethylphenyl) afforded [PtL(FcPPB)] {L=CO ( 2 ) and CNXyl ( 3 )} featuring η2BC‐ and η1B‐arylborane coordination modes, respectively. Reaction of 1 or 2 with H2 yielded [PtH(μ‐H)(FcPPB)] in which the borane is bound to a hydride ligand on platinum. Addition of PhC2H to [Pt(FcPPB)] afforded [Pt(C2Ph)(μ‐H)(FcPPB)] ( 5 ), which rapidly converted to [Pt(FcPPB′)] ( 6 ; FcPPB′=[Fe(η5‐C5H4PPh2)(η5‐C5H4PtBu{C6H4(BPh‐CPh=CHPh‐Z)‐ortho}]) in which the newly formed vinylborane is η3BCC‐coordinated. Unlike arylborane complex 1 , vinylborane complex 6 does not react with CO, CNXyl, H2 or HC2Ph at room temperature. 相似文献
14.
Transition Metal‐substituted Phosphaalkenes. 42 Reactivity of the Ferriophosphaalkenes [(η5‐C5Me5)(CO)2FeP=C(NR )R2] (NR = NMe2, NC5H10, R2 = Ph, t Bu) towards Protic Acids, Alkylation Reagents, and [{( Z )‐Cyclooctene}Cr(CO)5] The reaction of equimolar amounts of [(η5‐C5Me5)(CO)2FeP=C(NR )R2] ( 2 a : NR = NMe2, R2 = Ph; 2 b : NMe2. tBu; 2 c : NC5H10, Ph) and etherial HBF4 gave rise to the formation of [(η5‐C5Me5)(CO)2FeP(H)C(NR )R2] (BF4) ( 3 a – c ) which were isolated as light red powders. Compounds 2 a – c were converted into [(η5‐C5Me5)(CO)2FeP(Me)C(NR )R2] (SO3CF3) ( 4 a – c ) by treatment with methyl trifluoromethane sulfonate. In addition 2 a and Me3SiCH2OSO2CF3 afforded light red [(η5‐C5Me5)(CO)2FeP(CH2SiMe3)C(NMe2)Ph](SO3CF3) ( 5 ). The black complex [(η5‐C5Me5)(CO)2FeP{Cr(CO)5}C(NMe2)Ph] ( 6 ) resulted from the combination of 2 a with [{(Z)‐cyclooctene}Cr(CO)5]. The novel products were characterized by elemental analyses and spectra (IR, 1H‐, 13C‐ und 31P‐NMR). 相似文献
15.
Dr. Chi‐Shian Chen Yu‐Fang Lin Dr. Wen‐Yann Yeh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(4):936-940
Reactions of the open‐cage fullerene C63NO2(Py)(Ph)2 ( 1 ) with [Ru3(CO)12] produce [Ru3(CO)8(μ,η5‐C63NO2(Py)(Ph)2)] ( 2 ), [Ru2H(CO)3(μ,η7‐C63N(Py)(Ph)(C6H4))] ( 3 ), and [Ru(CO)(Py)2(η3‐C63NO2(Py)(Ph)2)] ( 4 ), in which the orifice sizes are modified from 12 to 8, 11, and 15‐membered ring, through ruthenium‐mediated C?O and C?C bond activation and formation. 相似文献
16.
Dr. Tetsuya Fukuda Dr. Hisako Hashimoto Prof. Dr. Shigeyoshi Sakaki Prof. Dr. Hiromi Tobita 《Angewandte Chemie (International ed. in English)》2016,55(1):188-192
Treatment of pyridine‐stabilized silylene complexes [(η5‐C5Me4R)(CO)2(H)W?SiH(py)(Tsi)] (R=Me, Et; py=pyridine; Tsi=C(SiMe3)3) with an N‐heterocyclic carbene MeIiPr (1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene) caused deprotonation to afford anionic silylene complexes [(η5‐C5Me4R)(CO)2W?SiH(Tsi)][HMeIiPr] (R=Me ( 1‐Me ); R=Et ( 1‐Et )). Subsequent oxidation of 1‐Me and 1‐Et with pyridine‐N‐oxide (1 equiv) gave anionic η2‐silaaldehydetungsten complexes [(η5‐C5Me4R)(CO)2W{η2‐O?SiH(Tsi)}][HMeIiPr] (R=Me ( 2‐Me ); R=Et ( 2‐Et )). The formation of an unprecedented W‐Si‐O three‐membered ring was confirmed by X‐ray crystal structure analysis. 相似文献
17.
Phosphanediyl Transfer from Inversely Polarized Phosphaalkenes R1P=C(NMe2)2 (R1 = tBu, Cy, Ph, H) onto Phosphenium Complexes [(η5‐C5H5)(CO)2M=P(R2)R3] (R2 = R3 = Ph; R2 = tBu, R3 = H; R2 = Ph, R3 = N(SiMe3)2) Reaction of the freshly prepared phosphenium tungsten complex [(η5‐C5H5)(CO)2W=PPh2] ( 3 ) with the inversely polarized phosphaalkenes RP=C(NMe2)2 ( 1 ) ( a : R = tBu; b : Cy; c : Ph) led to the η2‐diphosphanyl complexes ( 9a‐c ) which were isolated by column chromatography as yellow crystals in 24‐30 % yield. Similarly, phosphenium complexes [(η5‐C5H5)(CO)2M=P(H)tBu] (M = W ( 6 ); Mo ( 8 )) were converted into (M = W ( 11 ); Mo ( 12 )) by the formal abstraction of the phosphanediyl [PtBu] from 1a . Treatment of [(η5‐C5H5)(CO)2W=P(Ph)N(SiMe3)2] ( 4 ) with HP=C(NMe2)2 ( 1d ) gave rise to the formation of yellow crystalline ( 10 ). The products were characterized by elemental analyses and spectra (IR, 1H, 13C‐, 31P‐NMR, MS). The molecular structure of compound 10 was elucidated by an X‐ray diffraction analysis. 相似文献
18.
Harald Krautscheid Eberhard Matern Jolanta Olkowska‐Oetzel Jerzy Pikies Gerhard Fritz 《无机化学与普通化学杂志》2001,627(4):675-678
Coordination Chemistry of P‐rich Phosphanes and Silylphosphanes. XXII. The Formation of [η2‐{tBu–P=P–SiMe3}Pt(PR3)2] from (Me3Si)tBuP–P=P(Me)tBu2 and [η2‐{C2H4}Pt(PR3)2] (Me3Si)tBuP–P = P(Me)tBu2 reacts with [η2‐{C2H4}Pt(PR3)2] yielding [η2‐{tBu–P=P–SiMe3}Pt(PR3)2]. However, there is no indication for an isomer which would be the analogue to the well known [η2‐{tBu2P–P}Pt(PPh3)2]. The syntheses and NMR data of [η2‐{tBu–P=P–SiMe3}Pt(PPh3)2] and [η2‐{tBu–P=P–SiMe3}Pt(PMe3)2] as well as the results of the single crystal structure determination of [η2‐{tBu–P=P–SiMe3}Pt(PPh3)2] are reported. 相似文献
19.
Rare‐Earth‐Metal Methyl,Amide, and Imide Complexes Supported by a Superbulky Scorpionate Ligand
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Dorothea Schädle Dr. Cäcilia Maichle‐Mössmer Dr. Christoph Schädle Prof. Dr. Reiner Anwander 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(2):662-670
The reaction of monomeric [(TptBu,Me)LuMe2] (TptBu,Me=tris(3‐Me‐5‐tBu‐pyrazolyl)borate) with primary aliphatic amines H2NR (R=tBu, Ad=adamantyl) led to lutetium methyl primary amide complexes [(TptBu,Me)LuMe(NHR)], the solid‐state structures of which were determined by XRD analyses. The mixed methyl/tetramethylaluminate compounds [(TptBu,Me)LnMe({μ2‐Me}AlMe3)] (Ln=Y, Ho) reacted selectively and in high yield with H2NR, according to methane elimination, to afford heterobimetallic complexes: [(TptBu,Me)Ln({μ2‐Me}AlMe2)(μ2‐NR)] (Ln=Y, Ho). X‐ray structure analyses revealed that the monomeric alkylaluminum‐supported imide complexes were isostructural, featuring bridging methyl and imido ligands. Deeper insight into the fluxional behavior in solution was gained by 1H and 13C NMR spectroscopic studies at variable temperatures and 1H–89Y HSQC NMR spectroscopy. Treatment of [(TptBu,Me)LnMe(AlMe4)] with H2NtBu gave dimethyl compounds [(TptBu,Me)LnMe2] as minor side products for the mid‐sized metals yttrium and holmium and in high yield for the smaller lutetium. Preparative‐scale amounts of complexes [(TptBu,Me)LnMe2] (Ln=Y, Ho, Lu) were made accessible through aluminate cleavage of [(TptBu,Me)LnMe(AlMe4)] with N,N,N′,N′‐tetramethylethylenediamine (tmeda). The solid‐state structures of [(TptBu,Me)HoMe(AlMe4)] and [(TptBu,Me)HoMe2] were analyzed by XRD. 相似文献
20.
From Dibismuthenes to Three‐ and Two‐Coordinated Bismuthinidenes by Fine Ligand Tuning: Evidence for Aromatic BiC3N Rings through a Combined Experimental and Theoretical Study
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Iva Vránová Dr. Mercedes Alonso Dr. Rabindranath Lo Dr. Robert Sedlák Dr. Roman Jambor Prof. Aleš Růžička Prof. Frank De Proft Prof. Pavel Hobza Dr. Libor Dostál 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(47):16917-16928
The reduction of N,C,N‐chelated bismuth chlorides [C6H3‐2,6‐(CH?NR)2]BiCl2 [where R=tBu ( 1 ), 2′,6′‐Me2C6H3 ( 2 ), or 4′‐Me2NC6H4 ( 3 )] or N,C‐chelated analogues [C6H2‐2‐(CH?N‐2′,6′‐iPr2C6H3)‐4,6‐(tBu)2]BiCl2 ( 4 ) and [C6H2‐2‐(CH2NEt2)‐4,6‐(tBu)2]BiCl2 ( 5 ) is reported. Reduction of compounds 1 – 3 gave monomeric N,C,N‐chelated bismuthinidenes [C6H3‐2,6‐(CH?NR)2]Bi [where R=tBu ( 6 ), 2′,6′‐Me2C6H3 ( 7 ) or 4′‐Me2NC6H4 ( 8 )]. Similarly, the reduction of 4 led to the isolation of the compound [C6H2‐2‐(CH?N‐2′,6′‐iPr2C6H3)‐4,6‐(tBu)2]Bi ( 9 ) as an unprecedented two‐coordinated bismuthinidene that has been structurally characterized. In contrast, the dibismuthene {[C6H2‐2‐(CH2NEt2)‐4,6‐(tBu)2]Bi}2 ( 10 ) was obtained by the reduction of 5 . Compounds 6 – 10 were characterized by using 1H and 13C NMR spectroscopy and their structures, except for 7 , were determined with the help of single‐crystal X‐ray diffraction analysis. It is clear that the structure of the reduced products (bismuthinidene versus dibismuthene) is ligand‐dependent and particularly influenced by the strength of the N→Bi intramolecular interaction(s). Therefore, a theoretical survey describing the bonding situation in the studied compounds and related bismuth(I) systems is included. Importantly, we found that the C3NBi chelating ring in the two‐coordinated bismuthinidene 9 exhibits significant aromatic character by delocalization of the bismuth lone pair. 相似文献