摘要:

1,2,3‐Triborolanes from Norbornene Derivatives, Allylbenzene and Dehalogenation Products of Dichloro(diisopropyl‐amino)borane; 2,4,5‐Tris(diisopropylamino)‐2,4,5‐triborabicyclo[1.1.1]pentane‐Bicyclus or Carborane?The new 1,2,3‐tris(diisopropylamino)triborolanes1, 2, 3and4have been prepared by treatment of mixtures of 2‐norbornene (A), 5‐methylene‐2‐norbornene (B), 5‐ethylidene‐2‐norbornene (C) and allylbenzene (D) with dichloro(diisopropylamino)borane with Na/K alloy in hexane. The corresponding species5, derived from 2,5‐norbornadiene (E), is relatively unstable and by a retro Diels‐Alder reaction gives 2,3,4‐tris(diisopropylamino)‐1,5‐dicarba‐closo‐pentaborane(5) (6). The compounds are characterized by chemical analyses, MS and NMR (1H,11B,13C,15N) an

ISSN:0009-2940    

DOI:10.1002/cber.19911241202

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

1,3‐Bis[tert‐butyl(di‐tert‐butylfluorosilyl)amino]trisulfane – a Compound with FSiNSSSNSiF HelixThe lithium derivative oftert‐butyl(di‐tert‐butylfluorosilyl)‐amine (1) reacts with sulfur or selenium to give the bis[(fluorosilyl)‐amino]di‐ and ‐trisulfanes2, 3and ‐selane4, respectively. The trisulfane3crystallizes fromn‐hexane and exhibits a helical

ISSN:0009-2940    

DOI:10.1002/cber.19911241203

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Syntheses and Structures of Cyclic and Acyclic Compounds Containing Vanadium(V) and Molybdenum(VI)The reaction of (C2F5)2P(Cl)NSiMe3(2) with Cl3VNSiMe3in CH2Cl2yields the eight‐membered ring [(C2F5)2PN2VCl2]2(3). (CF3)2P(Cl)NSiMe3(1) reacts with VOCl3to form the eight‐membered ring [(CF3)2PN]3NVCl2(4). A six‐membered ring [Ph2PN]2NVCl2(5) can be isolated from the reaction of Ph2P(Cl)NSiMe3with VOCl3.1reacts quantitatively with MoO2Cl2and MoOCl4to form [MoOCl3‐O‐P(CF3)2N‐SiMe3]4(6) and (CF3)2P(Cl)N‐MoOCl3(7), respectively. The molecular structures of3, 5, and6have been determ

ISSN:0009-2940    

DOI:10.1002/cber.19911241204

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

New Cyclooctatetraene Complexes of Niobium[1]The (butadiene)niobium complexes Cp′Nb(C4H6)2and Cp′Nb(C4H6)(PMe3)2(Cp′C5H4Me) react with cyclooctatetraene (COT) to give Cp′Nb(C4H6)(COT) (2), Cp′Nb(COT)2(3), and Cp′Nb(PMe3)2(COT) (5) with fluxional COT ligands. The structure of3exhibits aprone‐η3‐ and asupine‐η4‐COT ligand which interchange their role at elevated temperature. That of5shows

ISSN:0009-2940    

DOI:10.1002/cber.19911241205

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

1,6‐Heptadiene Nickel(0) Complexes:rac/meso‐(μ‐η2,η2‐C7{Ni(η2,η2‐C7H12)}2und L‐Ni(η2,η2‐C7H12)Ni(CDT) dissolves in 1,6‐heptadiene with displacement of the CDT to yield the dinuclear homoleptic productrac/meso‐(μ‐ η2,η2‐C7H12){Ni(η2, η2‐C7H12)}2(1) as a mixture of stereoisomers, in which the nickel atoms are trigonal‐planar coordinated by a chelating 1,6‐diene ligand and one CC bond of a bridging diene ligand. The stereoisomers differ in the coordination mode of the bridging diene ligand.‐The bridging diene ligand in1can be displaced by various donor/acceptor molecules. In pentane,1reacts with ethene to yield a solution of mononuclear (C2H4)Ni(η2,η2‐C7H12) (2). With alkynes unstable complexes are formed of which the anticipated ethyne derivative (C2H2)Ni(η2,η2‐C7H12) (3) decomposes explosively at – 100°C. With isocyanides, methylenephosphoranes, methyllithium, amines, pyridines, phosphanes, and phosphites (i.e. C, N, P donors) crystalline complexes of type L‐Ni(η2.η2C7H12) have been obtained, of which the derivatives with L=tBuN  C 4, Me3PCH25, LiCH36, C7H13N7, C5H5N8, Me3P9,iPr3P10, Ph3P11, (PhO)3P12are charac

ISSN:0009-2940    

DOI:10.1002/cber.19911241206

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

C‐Halophosphaalkenes (1, 2) were prepared in high yield by a one‐pot synthesis from HCX3or CI4and Mes* PCl2(Mes*  supermesityl  2,4,6‐tri‐tert‐butylphenyl). The C‐iodophosphaalkenes Mes* P  Cl2(1 C) and Mes*P  CHI (2c) undergo halogen‐metal exchange withn‐BuLi at low temperatures. The resulting carbenoids Mes*P  CILi (11 c) and Mes*P  CHLi (6) reacted with ClMMe3(M  Si, Ge, Sn) to give Mes*PCIMMe3[(Z)‐13: M  Ge; (Z)‐14: M  Sn] or Mes*P  CHMMe3(8–10), respectively. Further reaction of (Z)‐13and (Z)‐14withnBuLi and ClMMe3gave Mes*PC(MMe3(18: MGe;19: M  Sn). The carbenoid (Z)‐11 cdecomposed at −85°C; instead of the expected “phosphaisonitrile” Mes*P  C : (21), only Mes*CP (15) was obtained which lends ex

ISSN:0009-2940    

DOI:10.1002/cber.19911241207

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Complexation of 1, 3‐Dihydro‐1, 3, 10, 10‐tetramethyl‐1, 3‐dibora‐4, 5‐benzopentafulvene with Fe(CO)3and CpCo Fragments: Synthesis, Crystal and Electronic Structure of Tricarbonyl[(η5‐cyclopentadienyl)cobalt][μ,η5:η4‐(1, 3‐dihydro‐1, 3, 10, 10‐tetramethyl‐1, 3‐dibora‐4, 5‐benzopentafulvene)]ironReaction of the 1, 3‐dibora‐4, 5‐benzopentafulvene1with the isolobal organometallic fragments Co(C5H5) and Fe(CO)3leads to the slipped triple‐decker complex5. It is also formed when2is stacked with the Co(C5H5) fragment. The X‐ray structure analysis of5reveals that the Co(C5H5) fragment is coordinated to the 1, 3‐diborole ring, and the Fe(CO)3group interacts with the Y‐shaped B2CC unit. An MO calculation indicates that the formation of5occurs by distortion of2(η5‐ → η4‐bonding) and complexation of the Co(C5H5) gr

ISSN:0009-2940    

DOI:10.1002/cber.19911241208

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Abstract[Ru2(μ‐O2CCH3)4(O2CCH3)] reacts with excess triphenylphosphane in acetic acid to givefac‐[Ru(O2CCH3)2(PPh3)3] · 2CH3CO2H (1), which crystallizes in the triclinic space group P 1−with Z=2. The three phosphane ligands are in the sterically congested facial configuration, and the distorted octahedral geometry around the metal is completed by a unidentate and chelating acetate. A variable temperature31P{1H}‐NMR study of the complex in CH2Cl2showed the three phosphanes to be inequivalent at low temperature. On raising the temperature two separate coalescence processes are observed, ultimately making all of the phosphanes equivalent at room temperature. Complex1shows slight catalytic activity for the ring‐opening polymerization of bicyclo[2.2.1]hept‐2‐e

ISSN:0009-2940    

DOI:10.1002/cber.19911241209

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Azoalkane‐ und Nitrene‐Bridged Carbonyl Metal Clusters of Iron and RutheniumBy using cluster buildup reactions, the new azoalkane‐bridged clusters Ru3(CO)9(RNNR) (3a, RMe,3b, REt), Fe2Ru(CO)9(EtNNEt) (4), Ru4(CO)12(RNNR) (5a, RMe,5b, REt), and FeRu3(CO)12(EtNNEt) (6) were obtained. Upon attempts to prepare further such compounds, the N‐N bond was cleaved resulting in nitrene‐bridged clusters including the new compound Fe4(CO)11(μ4‐NEt)2(9). Cluster buildup starting from Ru3(CO)9(μ3‐NPh)2resulted in Ru4(CO)11(μ4‐NPh)2(10) and FeRu3(CO)11(μ4‐NPh)2(11). The crystal structures of5band9as well as some reactions of the n

ISSN:0009-2940    

DOI:10.1002/cber.19911241210

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Compounds with the 2,4‐Dimethyl‐2,4‐diaza‐1,5‐diphosphapentan‐3‐one Skeleton; Synthesis, Structure, and Properties of 1,5‐Di‐tert‐butyl‐2,4‐dimethyl‐1,5‐diphenyl‐2,4‐diaza‐1,5‐diphosphapentan‐3‐one and Its DerivativesN,N′‐Dimethyl‐N‐N′‐bis(trimethylsilyl)urea (1) reacts withtert‐butylchlorophenylphosphane (2) to form the monophosphino/ trimethylsilyl‐substituted urea3. Under more vigorous conditions the bisphosphino‐substituted derivative4was also obtained. The reaction of 4 with the tetracarbonyl norbornadiene derivatives of Cr, Mo, and W furnished the unusual chelate complexes5–7, in which the ligand4is coordinated to the metal through one of the two phosphorus atoms and the oxygen atom of the carbonyl group. The free ligand4and the isostructural complexes5and6were subjected to X‐ray structure analyses. The approximate twofold symmetry of4is lost as a result of a major conformational change on complex formation. In contrast,4reacts with Fe2(CO)9and with (COD)‐PtCl2(COD=1,5‐cyclooctadiene) to give the complexes8and9. In both8and9the ligand4is coordinated by both phosphorus atoms. Reaction of4with sulfur and selenium led to the disulfide10

ISSN:0009-2940    

DOI:10.1002/cber.19911241211

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY