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1.
New Trinuclear Complexes of Group 6, 8, and 9 Metals with a Triply Bridging Borylene Ligand 下载免费PDF全文
K. Yuvaraj Moulika Bhattacharyya Rini Prakash V. Ramkumar Prof. Dr. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(26):8889-8896
Trinuclear complexes of group 6, 8, and 9 transition metals with a (μ3‐BH) ligand [(μ3‐BH)(Cp*Rh)2(μ‐CO)M′(CO)5], 3 and 4 ( 3 : M′=Mo; 4 : M′=W) and 5 – 8 , [(Cp*Ru)3(μ3‐CO)2(μ3‐BH)(μ3‐E)(μ‐H){M′(CO)3}] ( 5 : M′=Cr, E=CO; 6 : M′=Mo, E=CO; 7 : M′=Mo, E=BH; 8 : M′=W, E=CO), have been synthesized from the reaction between nido‐[(Cp*M)2B3H7] (nido‐ 1 : M=Rh; nido‐ 2 : M=RuH, Cp*=η5‐C5Me5) and [M′(CO)5 ? thf] (M′=Mo and W). Compounds 3 and 4 are isoelectronic and isostructural with [(μ3‐BH)(Cp*Co)2(μ‐CO)M′(CO)5], (M′=Cr, Mo and W) and [(μ3‐BH)(Cp*Co)2(μ‐CO)(μ‐H)2M′′H(CO)3], (M′′=Mn and Re). All compounds are composed of a bridging borylene ligand (B?H) that is effectively stabilized by a trinuclear framework. In contrast, the reaction of nido‐ 1 with [Cr(CO)5 ? thf] gave [(Cp*Rh)2Cr(CO)3(μ‐CO)(μ3‐BH)(B2H4)] ( 9 ). The geometry of 9 can be viewed as a condensed polyhedron composed of [Rh2Cr(μ3‐BH)] and [Rh2CrB2], a tetrahedral and a square pyramidal geometry, respectively. The bonding of 9 can be considered by using the polyhedral fusion formalism of Mingos. All compounds have been characterized by using different spectroscopic studies and the molecular structures were determined by using single‐crystal X‐ray diffraction analysis. 相似文献
2.
Shubhankar Kumar Bose K. Geetharani V. Ramkumar Shaikh M. Mobin Sundargopal Ghosh Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(48):13483-13490
Reaction of [CpnMCl4?x] (M=V: n=x=2; M=Nb: n=1, x=0) or [Cp*TaCl4] (Cp=η5‐C5H5, Cp*=η5‐C5Me5), with [LiBH4?thf] at ?70 °C followed by thermolysis at 85 °C in the presence of [BH3?thf] yielded the hydrogen‐rich metallaboranes [(CpM)2(B2H6)2] ( 1 : M=V; 2 : M = Nb) and [(Cp*Ta)2(B2H6)2] ( 3 ) in modest to high yields. Complexes 1 and 3 are the first structurally characterized compounds with a metal–metal bond bridged by two hexahydroborate (B2H6) groups forming a symmetrical complex. Addition of [BH3?thf] to 3 results in formation of a metallaborane [(Cp*Ta)2B4H8(μ‐BH4)] ( 4 ) containing a tetrahydroborate ligand, [BH4]?, bound exo to the bicapped tetrahedral cage [(Cp*Ta)2B4H8] by two Ta‐H‐B bridge bonds. The interesting structural feature of 4 is the coordination of the bridging tetrahydroborate group, which has two B? H bonds coordinated to the tantalum atoms. All these new metallaboranes have been characterized by mass, 1H, 11B, and 13C NMR spectroscopy and elemental analysis and the structural types were established unequivocally by crystallographic analysis of 1 – 4 . 相似文献
3.
Rajendra Singh Dhayal Kiran Kumar Varma Chakrahari V. Ramkumar Sundargopal Ghosh 《Journal of Cluster Science》2009,20(3):565-572
Abstract Reaction of [(η5-C5Me5Mo)2B5H9], 1 with 5-fold excess of n-BuLi at −70 °C followed by excess of RI (R = n-Bu or Ph) at room temperature yielded B-R inserted metallaboranes [(η5-C5Me5Mo)2B5H8R] (2: R = n-Bu, 5: R = Ph), [(η5-C5Me5Mo)2B5H7R2] (3, 4: R = n-Bu; 6, 7: R = Ph). Isolated yields of mono-alkyl/arylated species are better than di-alkyl/arylated ones. All the new cluster compounds have been characterized by IR, 1H, 11B, 13C NMR and mass spectroscopy as simple substitution derivatives of [(η5-C5Me5Mo)2B5H9] and the structural types of one of these species, 2 was established by X-ray crystallographic analysis.
Graphical Abstract Reaction of [(η5-C5Me5Mo)2B5H9], with 5-fold excess of n-BuLi at −70 °C followed by excess of RI (R = n-Bu or Ph) at room temperature yielded B-R inserted metallaboranes [(η5-C5Me5Mo)2B5H9-nRn] (When R = n-Bu, n = 2, 1; R = Ph, n = 2, 1).
相似文献
4.
Synthesis,Structure, Bonding,and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] and [{Cp*M(CO)2}2B2H2M(CO)4], M=Mo,W 下载免费PDF全文
Dr. Bijan Mondal Ranjit Bag Sagar Ghorai Dr. K. Bakthavachalam Prof. Eluvathingal D. Jemmis Prof. Sundargopal Ghosh 《Angewandte Chemie (International ed. in English)》2018,57(27):8079-8083
The reaction of [(Cp*Mo)2(μ‐Cl)2B2H6] ( 1 ) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] ( 2 ). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged Cs structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum–alkyne complex [{CpMo(CO)2}2C2H2]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO)4] fragment, [{Cp*Mo(CO)2}2 B2H2W(CO)4] ( 3 ) was isolated upon treatment with [W(CO)5?thf]. Compound 3 shows the intriguing presence of [B2H2] with a short B?B length of 1.624(4) Å. We isolated the tungsten analogues of 3 , [{Cp*W(CO)2}2B2H2W(CO)4] ( 4 ) and [{Cp*W(CO)2}2B2H2Mo(CO)4] ( 5 ), which provided direct proof of the existence of the tungsten analogue of 2 . 相似文献
5.
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2018,130(27):8211-8215
The reaction of [(Cp*Mo)2(μ‐Cl)2B2H6] ( 1 ) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] ( 2 ). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged Cs structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum–alkyne complex [{CpMo(CO)2}2C2H2]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO)4] fragment, [{Cp*Mo(CO)2}2 B2H2W(CO)4] ( 3 ) was isolated upon treatment with [W(CO)5⋅thf]. Compound 3 shows the intriguing presence of [B2H2] with a short B−B length of 1.624(4) Å. We isolated the tungsten analogues of 3 , [{Cp*W(CO)2}2B2H2W(CO)4] ( 4 ) and [{Cp*W(CO)2}2B2H2Mo(CO)4] ( 5 ), which provided direct proof of the existence of the tungsten analogue of 2 . 相似文献
6.
Chemistry of Diruthenium and Dirhodium Analogues of Pentaborane(9): Synthesis and Characterization of Metal N,S‐Heterocyclic Carbene and B‐Agostic Complexes 下载免费PDF全文
M. Sc. Dipak Kumar Roy M. Sc. Bijan Mondal M. Sc. R. S. Anju Prof. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(9):3640-3648
Building upon our earlier results on the synthesis of electron‐precise transition‐metal–boron complexes, we continue to investigate the reactivity of pentaborane(9) and tetraborane(10) analogues of ruthenium and rhodium towards thiazolyl and oxazolyl ligands. Thus, mild thermolysis of nido‐[(Cp*RuH)2B3H7] ( 1 ) with 2‐mercaptobenzothiazole (2‐mbtz) and 2‐mercaptobenzoxazole (2‐mboz) led to the isolation of Cp*‐based (Cp*=η5‐C5Me5) borate complexes 5 a , b [Cp*RuBH3L] ( 5 a : L=C7H4NS2; 5 b : L=C7H4NOS)) and agostic complexes 7 a , b [Cp*RuBH2(L)2], ( 7 a : L=C7H4NS2; 7 b : L=C7H4NOS). In a similar fashion, a rhodium analogue of pentaborane(9), nido‐[(Cp*Rh)2B3H7] ( 2 ) yielded rhodaboratrane [Cp*RhBH(L)2], 10 (L=C7H4NS2). Interestingly, when the reaction was performed with an excess of 2‐mbtz, it led to the formation of the first structurally characterized N,S‐heterocyclic rhodium‐carbene complex [(Cp*Rh)(L2)(1‐benzothiazol‐2‐ylidene)] ( 11 ) (L=C7H4NS2). Furthermore, to evaluate the scope of this new route, we extended this chemistry towards the diruthenium analogue of tetraborane(10), arachno‐[(Cp*RuCO)2B2H6] ( 3 ), in which the metal center possesses different ancillary ligands. 相似文献
7.
Nicholas Arleth Michael T. Gamer Ralf K?ppe Nikolay A. Pushkarevsky Sergey N. Konchenko Martin Fleischmann Michael Bodensteiner Manfred Scheer Peter W. Roesky 《Chemical science》2015,6(12):7179-7184
The first 4d/4f polyphosphides were obtained by reaction of the divalent metallocenes [Cp*2Ln(thf)2] (Ln = Sm, Yb) with [{CpMo(CO)2}2(μ,η2:2-P2)] or [Cp*Mo(CO)2(η3-P3)]. Treatment of [Cp*2Ln(thf)2] (Ln = Sm, Yb) with [{CpMo(CO)2}2(μ,η2:2-P2)] gave the 16-membered bicyclic compounds [(Cp2*Ln)2P2(CpMo(CO)2)4] (Ln = Sm, Yb) as the major products. From the reaction involving samarocene, the cyclic P4 complex [(Cp*2Sm)2P4(CpMo(CO)2)2] and the cyclic P5 complex [(Cp*2Sm)3P5(CpMo(CO)2)3] were also obtained as minor products. In each reaction, the P2 unit is reduced and a rearrangement occurred. In dedicated cases, a P–P bond formation takes place, which results in a new aggregation of the central phosphorus scaffold. In the reactions of [Cp*2Ln(thf)2] (Ln = Sm, Yb) with [Cp*Mo(CO)2P3] a new P–P bond is formed by reductive dimerization and the 4d/4f hexaphosphides [(Cp*2Ln)2P6(Cp*Mo(CO)2)2] (Ln = Sm, Yb) were obtained. 相似文献
8.
D. A. Loginov A. V. Vologzhanina P. V. Petrovskii M. M. Vinogradov A. R. Kudinov 《Russian Chemical Bulletin》2008,57(8):1653-1656
The reaction of the iodide complex [(η5-C9H2Me5)RhI2]2 (1) or the acetonitrile complex [(η5-C9H2Me5)Rh(MeCN)3]2+ with Tl[Tl(η-7,8-C2B9H11)] afforded rhodacarborane (η5-C9H2Me5)Rh(7,8-C2B9H11) (2). The cationic triple-decker complex with the bridging boratabenzene ligand [Cp*Fe(μ-η:η-C5H3Me2BMe)Rh(η5-C9H2Me5)]2+ (3) was synthesized by the reaction of the nitromethane solvate [(η5-C9H2Me5)Rh(MeNO2)3]2+ with the sandwich compound Cp*Fe(η-C5H3Me2BMe). The structure of 2 was established by X-ray diffraction.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1623–1625, August, 2008. 相似文献
9.
Dr. Xian‐Kuan Huo Ge Su Prof. Dr. Guo‐Xin Jin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(39):12017-12027
Monophosphine‐o‐carborane has four competitive coordination modes when it coordinates to metal centers. To explore the structural transitions driven by these competitive coordination modes, a series of monophosphine‐o‐carborane Ir,Rh complexes were synthesized and characterized. [Cp*M(Cl)2{1‐(PPh2)‐1,2‐C2B10H11}] (M=Ir ( 1 a ), Rh ( 1 b ); Cp*=η5‐C5Me5), [Cp*Ir(H){7‐(PPh2)‐7,8‐C2B9H11}] ( 2 a ), and [1‐(PPh2)‐3‐(η5‐Cp*)‐3,1,2‐MC2B9H10] (M=Ir ( 3 a ), Rh ( 3 b )) can be all prepared directly by the reaction of 1‐(PPh2)‐1,2‐C2B10H11 with dimeric complexes [(Cp*MCl2)2] (M=Ir, Rh) under different conditions. Compound 3 b was treated with AgOTf (OTf=CF3SO3?) to afford the tetranuclear metallacarborane [Ag2(thf)2(OTf)2{1‐(PPh2)‐3‐(η5‐Cp*)‐3,1,2‐RhC2B9H10}2] ( 4 b ). The arylphosphine group in 3 a and 3 b was functionalized by elemental sulfur (1 equiv) in the presence of Et3N to afford [1‐{(S)PPh2}‐3‐(η5‐Cp*)‐3,1,2‐MC2B9H10] (M=Ir ( 5 a ), Rh ( 5 b )). Additionally, the 1‐(PPh2)‐1,2‐C2B10H11 ligand was functionalized by elemental sulfur (2 equiv) and then treated with [(Cp*IrCl2)2], thus resulting in two 16‐electron complexes [Cp*Ir(7‐{(S)PPh2}‐8‐S‐7,8‐C2B9H9)] ( 6 a ) and [Cp*Ir(7‐{(S)PPh2}‐8‐S‐9‐OCH3‐7,8‐C2B9H9)] ( 7 a ). Compound 6 a further reacted with nBuPPh2, thereby leading to 18‐electron complex [Cp*Ir(nBuPPh2)(7‐{(S)PPh2}‐8‐S‐7,8‐C2B9H10)] ( 8 a ). The influences of other factors on structural transitions or the formation of targeted compounds, including reaction temperature and solvent, were also explored. 相似文献
10.
Haijun Hao Herbert W. Roesky Chunming Cui Hans‐Georg Schmidt Mathias Noltemeyer Peihua Yu Guangcai Bai 《无机化学与普通化学杂志》2000,626(2):368-373
Treating [Cp*V(μ‐Cl)2]3 (Cp* = C5Me5) and [(2,6‐i‐Pr2C6H3N)2MoMe2], respectively, with Me3SnF afforded the title compounds [Cp*V(μ‐F)2]4 ( 1 ) and [(2,6‐i‐Pr2C6H3N)2MoF2] · THF ( 2 ). 1 has a tetrameric structure, in which four V atoms can be regarded as being arranged at the vertices of a distorted tetrahedron, with four long edges bridged by one F atom and each of the other two short edges bridged by two F atoms with a mean V–F bond length of 2.00 Å. A hydrolyzed product of 2 , [(2,6‐i‐Pr2C6H3N)6Mo4(μ3‐F)2Me2(μ‐O)4] ( 3 ) was characterized by elemental analyses and X‐ray single crystal study. The X‐ray diffraction analysis reveals that 3 has a unique tetranuclear structure, containing two five and two six coordinated Mo atoms connecting each other by four μ‐O and two μ3‐F atoms. The geometries around the two Mo atoms can be described having distorted trigonal bipyramidal and distorted octahedral coordination spheres, respectively. The Mo–(μ‐O) bond lengths are 1.813 Å (average) for five coordinated Mo atoms and 2.030 Å (average) for those of six coordinated, respectively, indicating an additional π bonding between five coordinated Mo atoms and the μ‐O atoms. The Mo–(μ3‐F) distances range from 2.291 to 2.352 Å. 相似文献
11.
D. A. Loginov M. M. Vinogradov D. S. Perekalin Z. A. Starikova K. A. Lyssenko P. V. Petrovskii A. R. Kudinov 《Russian Chemical Bulletin》2006,55(1):84-88
The reaction of the [(η-9-SMe2-7,8-C2B9H10)IrBr2]2 complex with Tl[Tl(η-7,8-C2B9H11)] afforded the iridacarborane compound (η-9-SMe2-7,8-C2B9H10)Ir(η-7,8-C2B9H11). The cationic complex [Cp*Ir(η-9-SMe2-7,8-C2B9H10)]+PF6
− (5 · PF6, Cp* is pentamethylcyclopentadienyl) was synthesized by the reaction of [Cp*IrCl2]2 with Na[9-SMe2-7,8-C2B9H10]. The structures of (η-9-SMe2-7,8-C2B9H10)Ir(η-cod) (cod is 1,5-cyclooctadiene) and 5 · PF6 were established by X-ray diffraction.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 81–84, January, 2006. 相似文献
12.
Dr. Nicholas Arleth Dr. Michael T. Gamer Dr. Ralf Köppe Prof. Dr. Sergey N. Konchenko Martin Fleischmann Prof. Dr. Manfred Scheer Prof. Dr. Peter W. Roesky 《Angewandte Chemie (International ed. in English)》2016,55(4):1557-1560
Reduction of [Cp*Fe(η5‐As5)] with [Cp′′2Sm(thf)] (Cp′′=η5‐1,3‐(tBu)2C5H3) under various conditions led to [(Cp′′2Sm)(μ,η4:η4‐As4)(Cp*Fe)] and [(Cp′′2Sm)2As7(Cp*Fe)]. Both compounds are the first polyarsenides of the rare‐earth metals. [(Cp′′2Sm)(μ,η4:η4‐As4)(Cp*Fe)] is also the first d/f‐triple decker sandwich complex with a purely inorganic planar middle deck. The central As42? unit is isolobal with the 6π‐aromatic cyclobutadiene dianion (CH)42?. [(Cp′′2Sm)2As7(Cp*Fe)] contains an As73? cage, which has a norbornadiene‐like structure with two short As?As bonds in the scaffold. DFT calculations confirm all the structural observations. The As?As bond order inside the cyclo As4 ligand in [(Cp′′2Sm)(μ,η4:η4‐As4)(Cp*Fe)] was estimated to be in between an As?As single bond and a formally aromatic As42? system. 相似文献
13.
Ravi Yadav Thomas Simler Bhupendra Goswami Christoph Schoo Ralf Kppe Subhayan Dey Peter W. Roesky 《Angewandte Chemie (International ed. in English)》2020,59(24):9443-9447
A route to directly access mixed Al–Fe polyphosphide complexes was developed. The reactivity of pentaphosphaferrocene, [Cp*Fe(η5‐P5)] (Cp*=C5Me5), with two different low‐valent aluminum compounds was investigated. The steric and electronic environment around the [AlI] centre are found to be crucial for the formation of the resulting Al–Fe polyphosphides. Reaction with the sterically demanding [Dipp‐BDIAlI] (Dipp‐BDI={[2,6‐iPr2C6H3NCMe]2CH}?) resulted in the first Al‐based neutral triple‐decker type polyphosphide complex. For [(Cp*AlI)4], an unprecedented regioselective insertion of three [Cp*AlIII]2+ moieties into two adjacent P?P bonds of the cyclo‐P5 ring of [Cp*Fe(η5‐P5)] was observed. The regioselectivity of the insertion reaction could be rationalized by isolating an analogue of the reaction intermediate stabilized by a strong σ‐donor carbene. 相似文献
14.
D. A. Loginov M. M. Vinogradov Z. A. Starikova P. V. Petrovskii A. R. Kudinov 《Russian Chemical Bulletin》2007,56(11):2162-2165
The visible light irradiation of the [(η5-C6H7)Fe(η-C6H6)]+ cation (1) in acetonitrile resulted in the substitution of the benzene ligand to form the labile acetonitrile species [(η5-C6H7)Fe(MeCN)3]+ (2). The reaction of 1 with ButNC in MeCN produced the stable isonitrile complex [(η5-C6H7)Fe(ButNC)3]+ (3). The photochemical reaction of cation 1 with pentaphosphaferrocene Cp*Fe(η-cyclo-P5) afforded the triple-decker cation with the bridging pentaphospholyl ligand, [(η5-C6H7)Fe(μ-η:η-cyclo-P5)FeCp*]+ (4). The latter complex was also synthesized by the reaction of cation 2 with Cp*Fe(η-cyclo-P5). The structure of the complex [3]PF6 was established by X-ray diffraction.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2088–2091, November, 2007. 相似文献
15.
Jian-Long Xia Wei-Cheng Xiong Gang Chen Guang-Ao Yu Shan Jin Sheng-Hua Liu 《Transition Metal Chemistry》2009,34(4):389-393
Abstract Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H2O)(NBD)][BF4] (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2. The reaction of [Cp*Ru(H2O)(NBD)][BF4] with 1,4-diphenylbutadiyne generates the unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C9H8–Ph in addition to the organometallic compound [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4]. [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BPh4]2 is generated after the reaction of compound [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2 with Na[BPh4]. The structure of this compound was confirmed by X-ray diffraction. A possible approach to form Ph–C≡C–C9H8–Ph and [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4] is suggested.
Graphical Abstract Formal [2 + 2 + 2] addition reaction of [Cp*Ru(H2O)(NBD)]BF4 (NBD = norbornadiene) with 4,4′-Diethynylbiphenyl generates [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2. The reaction of [Cp*Ru(H2O)(NBD)][BF4] with 1,4-diphenylbutadiyne simply generates unusual [2 + 2 + 2] additional organic compound Ph–C≡C–C9H8–Ph in addition to the organometallic compound [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4]. [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BPh4]2 is generated after the reaction of compound [C9H9-η6-C6H4(RuCp*)–C6H4(RuCp*)-η6-C9H9][BF4]2 with Na[BPh4]. The structure of this compound was confirmed by X-ray diffraction. And the possible approach to form Ph–C≡C–C9H8–Ph and [Cp*Ru(η6-C6H5–C≡C–C≡C–Ph)][BF4] was suggested.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
16.
Hydrolysis of pure Sb(OPri)3 by sol–gel method followed by sintering at 500 °C yields microcrystallites of Sb2O3 (senarmonite phase). Under similar conditions bimetallic alkoxide, [NaSb(OPri)4], yields a mixture of binary oxides Sb2O3 and Sb2O4. Chemical modification of Sb(OPri)3 with oximes forms monomeric products of the type [Sb(OPri)3−n
{ON=C(CH3)R}
n
] {where R = CH3, n = 1 [1]; n = 2 [2]; n = 3 [3]; R = 2-C5H4N, n = 1 [4]; n = 2 [5]; n = 3 [6]; R = 2-C4H3O, n = 1 [7]; n = 2 [8]; n = 3 [9]; R = 2-C4H3S, n = 1 [10]; n = 2 [11]; n = 3 [12]}. The liquid products [1–3, 7
&
10] were purified by distillation while the solids by recrystallization. All these products were characterized by elemental
analyses, IR, NMR (1H and 13C{1H}) and representative derivatives [1], [2] and [3] by FAB mass studies. On the basis of these studies, a distorted pyramidal structure for all the derivatives may be assumed
in the solution state containing an end-on coordination of oximes with the metal atom. Hydrolysis of the distilled precursors
[1], [2] and [3] under sol–gel conditions yields pure nano-sized α-Sb2O4. All the oxides were characterized by XRD, SEM and EDX analysis exhibiting minimum particle size for the oxide obtained from
the precursor [3]. 相似文献
17.
Christoph O. Hollfelder Dr. Lars N. Jende Dr. Hans-Martin Dietrich Dr. Klaus Eichele Dr. Cäcilia Maichle-Mössmer Prof. Dr. Reiner Anwander 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7298-7302
When activated with fluorinated borate cocatalysts the trimetallic complexes [Cp*LnMe2]3 (Ln=Y, Lu; Cp*=C5Me5) promote efficiently the formation of high-cis polybutadiene. Respective polyisoprenes instead bear much less pronounced microstructures, but reveal crosslinked products at lower polymerization temperatures. Varying the amount of cocatalyst, the emerging active species were examined by NMR spectroscopic techniques (incl. 1H DOSY). The occurrence of donor-solvent and thermally induced degradation products of the highly reactive precatalyst [Cp*YMe2]3 and derived catalyst species was revealed by the elucidation of methylidene clusters [Cp*3Y3Me4(CH2)(thf)2] and [Cp*6Y6Me4(CH2)4], as well as [(Cp*Y)2Me2(N(Me)2(C6H4)]n[B(C6F5)4]n, implying a multimetallic active species. 相似文献
18.
K. Geetharani Shubhankar Kumar Bose Babu Varghese Dr. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(37):11357-11366
Reaction of [1,2‐(Cp*RuH)2B3H7] ( 1 ; Cp*=η5‐C5Me5) with [Mo(CO)3(CH3CN)3] yielded arachno‐[(Cp*RuCO)2B2H6] ( 2 ), which exhibits a butterfly structure, reminiscent of 7 sep B4H10. Compound 2 was found to be a very good precursor for the generation of bridged borylene species. Mild pyrolysis of 2 with [Fe2(CO)9] yielded a triply bridged heterotrinuclear borylene complex [(μ3‐BH)(Cp*RuCO)2(μ‐CO){Fe(CO)3}] ( 3 ) and bis‐borylene complexes [{(μ3‐BH)(Cp*Ru)(μ‐CO)}2Fe2(CO)5] ( 4 ) and [{(μ3‐BH)(Cp*Ru)Fe(CO)3}2(μ‐CO)] ( 5 ). In a similar fashion, pyrolysis of 2 with [Mn2(CO)10] permits the isolation of μ3‐borylene complex [(μ3‐BH)(Cp*RuCO)2(μ‐H)(μ‐CO){Mn(CO)3}] ( 6 ). Both compounds 3 and 6 have a trigonal‐pyramidal geometry with the μ3‐BH ligand occupying the apical vertex, whereas 4 and 5 can be viewed as bicapped tetrahedra, with two μ3‐borylene ligands occupying the capping position. The synthesis of tantalum borylene complex [(μ3‐BH)(Cp*TaCO)2(μ‐CO){Fe(CO)3}] ( 7 ) was achieved by the reaction of [(Cp*Ta)2B4H8(μ‐BH4)] at ambient temperature with [Fe2(CO)9]. Compounds 2 – 7 have been isolated in modest yield as yellow to red crystalline solids. All the new compounds have been characterized in solution by mass spectrometry; IR spectroscopy; and 1H, 11B, and 13C NMR spectroscopy and the structural types were unequivocally established by crystallographic analysis of 2 – 6 . 相似文献
19.
Chalcogen-stabilized dimolybdaboranes 3-5 (3: [(Cp∗Mo)2B4H5Se(Ph)], 4: [(Cp∗Mo)2B4H3Se2(SeCH2Ph)] and 5: [(Cp∗Mo)2B3H6(BSR)(μ-η1-SR)] (R = 2,6-(tBu)2-C6H2OH)) have been isolated from the mild pyrolysis of dichalcogenide ligands, RE-E‘R (R = Ph: E = S, E‘ = Se; R = CH2Ph, [2,6-(tBu)2-C6H2OH]: E = E‘ = Se, S) and [(Cp∗Mo)2B4H8], 2, an intermediate generated from the reaction of [Cp∗MoCl4] (1) (Cp∗ = η5-C5Me5), with [LiBH4.thf]. The geometry of [(Cp∗Mo)2B4H5Se(Ph)] is similar to that of [(Cp∗Mo)2B5H9], in which one BH3 unit on the open face is replaced by a triple bridged selenium atom. All the compounds have been characterized in solution by 1H, 11B, 13C NMR and IR spectroscopy and elemental analysis. The structural types were unequivocally established by X-ray crystallographic analysis of compounds 3-5. 相似文献
20.
Dipak Kumar Roy Dr. Shubhankar Kumar Bose K. Geetharani Kiran Kumar Varma Chakrahari Dr. Shaikh M. Mobin Dr. Sundargopal Ghosh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(32):9983-9991
The reaction of [CpnMCl4?x] (M=V: n=2, x=2; M=Nb: n=1, x=0; Cp=η5‐C5H5) with LiBH4 ? THF followed by thermolysis in the presence of dichalcogenide ligands E2R2 (E=S, Te; R=2,6‐(tBu)2‐C6H2OH, Ph) and 2‐mercaptobenzothiazole (C7H5NS2) yielded dimetallaheteroboranes [{CpV(μ‐TePh)}2(μ3‐Te)BH ? thf] ( 1 ), [(CpV)2(BH3S)2] ( 2 ), [(CpNb)2B4H10S] ( 3 ), [(CpNb)2B4H11S(tBu)2C6H2OH] ( 4 ), and [(CpNb)2B4H11TePh] ( 5 ). In cluster 1 , the V2BTe atoms define a tetrahedral framework in which the boron atom is linked to a THF molecule. Compound 2 can be described as a dimetallathiaborane that is built from two edge‐fused V2BS tetrahedron clusters. Cluster 3 can be considered as an edge‐fused cluster in which a trigonal‐bipyramidal unit (Nb2B2S) has been fused with a tetrahedral core (Nb2B2) by means of a common Nb2 edge. In addition, thermolysis of an in‐situ‐generated intermediate that was produced from the reaction of [Cp2VCl2] and LiBH4 ? THF with excess BH3 ? THF yielded oxavanadaborane [(CpV)2B3H8(μ3‐OEt)] ( 6 ) and divanadaborane cluster [(CpV)2B5H11] ( 7 ). Cluster 7 exhibits a nido geometry with C2v symmetry and it is isostructural with [(Cp*M)2B5H9+n] (M=Cr, Mo, and W, n=0; M=Ta, n=2; Cp*=η5‐C5Me5). All of these new compounds have been characterized by 1H NMR, 11B NMR, and 13C NMR spectroscopy and elemental analysis and the structural types were established unequivocally by crystallographic analysis of compounds 1 – 4 , 6 , and 7 . 相似文献