摘要:

AbstractVariouserythro‐ andthreo‐configurated dichloro[1‐(hydroxyphenyl)‐2‐phenyl‐1,2‐ethanediamine]platinum(II) complexes were synthesized with the hydroxy group located in either the 2‐, 3‐, or 4‐position of the phenyl ring (38–40). The diastereoisomeric 1‐(3‐hydroxyphenyl)‐2‐phenyl‐1,2‐ethanediamines (31,32) andthreo‐1‐(2‐hydroxyphenyl)‐2‐phenyl‐1,2‐ethanediamine (30) were obtained by reduction of the 1,2‐diazidoethanes and subsequent ether cleavage. The configuration of thethreo‐1,2‐diazido‐1‐(2‐methoxyphenyl)‐2‐phenylethane (5) was elucidated by X‐ray analysis. The reduction of theerythro‐1,2‐diaryl‐1,2‐diazidoethanes, substituted with a methoxy group inortho or paraposition, results in elimination reactions with formation of side products. The desired 1,2‐diaryl‐1,2‐ethanediamines were finally synthesized via either an aziridine derivative21or by reduction of the respective dioximes27, 28. The diamine li

ISSN:0009-2940    

DOI:10.1002/cber.19911241102

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Synthesis of 6,6,7,7,13,13,14,14‐Octamethyl‐6,7,13,14‐tetrasiladispiro[4.2.4.2] tetradeca‐1,3,9,11‐tetraene and Its Application in the Chemistry of π Complexes of p‐ and d‐Block ElementsThe title compound2can be synthesized either by reaction of ([C5H5SiMe2SiMe2C5H5]2‐2Li+) with XSiMe2SiMe2X or by an intermolecular nucleophilic substitution reaction between two molecules of ([XSiMe2SiMe2C5H5]‐Li+). Isomers of2with allylic hydrogen atoms arise from silatropic rearrangements and therefore show “cyclopentadiene reactivity”. Reaction of the monoanion of2with FeCl2yields the ferrocene4. From the reaction of the dianion of2with Me5C5RuCl, the binuclear ruthenium complex7with Si – Si bridges in 1,2‐position can be isolated; reactions with FeCl2or Me5C5Fe(acac), with Me5C5GeCl, with SnCl2, and with PbCl2, lead to the metallocenes6, 7, 8, and9; in all these complexes the disilane bridges are in 1,2‐position. The binuclear cobalt complex10, in which the cyclopentadienyl rings are connected with each other by disilane bridges in 1,3‐position, can be synthesized by the reaction of2with CO2(CO)8. The results of single‐crystal X‐ray structure analyses of6and10are presented. The possible conformatio

ISSN:0009-2940    

DOI:10.1002/cber.19911241103

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Multiple Bonds Between Main‐Group Elements and Transition Metals, XCVI. – Niobium and Tantalum Complexes Having Imido LigandsThe new niobium and tantalum complexes2band2cof formula M[N(SiMe3)2]2(NSiMe3)(OSiMe3) (M = Nb,b; Ta, c) are accessible by the reaction of the oxychlorides MOCl3with the lithium amide LiN[Si(CH3)3]2in 36 and 27% isolated yield, respectiv

ISSN:0009-2940    

DOI:10.1002/cber.19911241104

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

An Improved Preparation of Silyl‐ and Germylpotassium and Synthesis of SilylgermanesThe preparation of KSiH3and KGeH3is improved, and several syntheses of silylgermane, H3Si – GeH3, are described. A series of other potential processing gases for PE‐CVD is prepared: H3Ge – SiR1R2R3(R1, R2, R3= H, H, Me; H, H, Et; H, H,tBu; H, H, Ph; H, Me, Me; Et, Et, Et; H, Me, Ph; H, Me, GeH3). A new method for the preparation of silylgermanes by the reaction of silyl esters of sulfonic acids (RSO3H, R = C4,F9, Me, Ph) with KGeH3is r

ISSN:0009-2940    

DOI:10.1002/cber.19911241105

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Isocyanatosulfonium SaltsRR'SF2reacts with Me3SiNCO to give the correspondingN‐(fluoroformyl)sulfur imides FC(O)NSRR' [R = NMe2, R' = F (7); R' = CF3(9)]. From these AsF5abstracts F‐with formation of isocyanatosulfonium salts ONC—SRR' + AsF‐6[R = F, R' = CF3(6); R = NMe2, R' = F (8); R = NMe2, R' = CF3(10)]. The spectroscopic properties of the fluoroformyl derivatives and of the isocyanato salts are discussed. The structures of8and10are determined by X‐ray

ISSN:0009-2940    

DOI:10.1002/cber.19911241106

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Monomeric, Tetrameric, and Polymeric Sodium Fluorenide · S [S = Me2N(CH2)2N(Me)(CH2)2NMe2, Me2N(CH2)nNMe2(n = 2, 3)]The metallation of fluorene with sodium butanide (NanBu) in the presence of N bases yields solvated sodium fluorenide. Base adducts with bi‐ and tridentateN‐chelating ligands have been isolated: Na(fluorenide)(pmdta) (1[PMDTA = Me2N(CH2)2N(Me)(CH2)2NMe2], [Na(fluorenide)(tmeda)]n(2) [TMEDA = Me2N(CH2)2N(Me)(CH2)2NMe2], [Na(fluorenide)(tmeda)]4) (3) [TMPDA = Me2N(CH2)3NMe2]. According to X‐ray diffraction studies monomeric (1), polymeric (2), and cyclic‐tetrameric (3) structures are present in the crystal. These pronounced structural variations are explained on the basis of ionic contact aggregates where together with coulomb interactions the steric requirements of the ligands become rather important. Contact distances between Na ions and several C atoms of the carbanion may vary (ca. 260—300 pm) and definite coordination numbers become m

ISSN:0009-2940    

DOI:10.1002/cber.19911241107

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

AbstractThe (cyclopentadienyl)cobalt(I) complex4of the 4,7‐dihydroacepentaleneThe numbering of the ring system corresponds to the tricyclo‐decatetraene nomenclature used in the Exp. Part. Thus, 4,7‐substitution would be 2a,4a‐substitution in acepentalene numbering.derivative2bhas been prepared by the reaction of the ligand with (cyclopentadienyl)bis(ethene)cobalt(I). NOE experiments indicate a complexation at the convex face of the polyolefinic ligand.1H‐NMR spectra establish a degenerate haptotropic rearrangement with CpCo migration from one diene unit to the adjacent one. The activation energy of this process is estimated to be 15 kcal/mol. An X‐ray crystal structure determination of (η4‐4,7‐dihydroacepentalene)tricarbonyliron derivative3ashows a distorted coordination of Fe(CO)3at the convex face of

ISSN:0009-2940    

DOI:10.1002/cber.19911241108

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Metal Complexes of Biologically Important Ligands, LXIII1). — Aspartame as Tridendate Ligand in Organometallic Complexes: Preparation and Structure of Cp*Rh[O2CCH2CH(NH2)C(O)NCH(CH2Ph)CO2Me]Aspartame reacts with [Cp*RhCl2]2in the presence of base to give the title complex1with the deprotonated tridendate dipeptide ester as ligan

ISSN:0009-2940    

DOI:10.1002/cber.19911241109

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Hydrocarbon‐Bridged Metal Complexes, XXII1). – Addition of Anionic Fischer Carbene Complexes to Coordinated Unsaturated Hydrocarbons with C – C CouplingThe addition of [(OC)5MC(OMe)CH2]–(M = Cr,W) to the cationic complexes [(OC)5Re(C2H4)]+and [(OC)3M' (λ7‐C7H7)]+(M' = Cr, Mo) affords the bimetallic hydrocarbon‐bridged complexes (OC)5M = C(OMe)CH2CH2CH2Re(CO)5(1) and (OC)5M = C(OMe)CH2C7H7– λ6– M'(CO)3(2), respectively. The structures of1aand2dhave been determined by

ISSN:0009-2940    

DOI:10.1002/cber.19911241110

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Reactions of the Azadiboriridines: Formation of Clusters and Ring Expansions*Nine bis(haloboryl)amines1were synthesized by haloboration of iminoboranes RB = NR” with dihaloboranes R'BHal2[R/R'/R” = Et/iPr/tBu (1b), Et/sBu/tBu (c),iPr/iPr/iPr (d),iPr/tBu/iPr (e),tBu/Me/tBu (g),tBu/Et/tBu (h),tBu/Et/SiMe3(k),tBu/tBu/SiMe3(1),tBu/Cl/tBun)]. The borane1ncan be transformed into1o(R' = NMe2) by the reaction with Me3SiNMe2; an equilibrium between1oand the four‐membered ring1o' is observed,1o' being formed from1oby intramolecular B – N coordination. On reduction with lithium, thenido‐diazahexaboranes3b–e,g,hare formed from the corresponding bis‐(haloboryl)amines1. In the case of3e,g,h, the ligands R and R' are unsymmetrically distributed to axial and equatorial positions of the fragment structure derived from the pentagonal bipyramid. In particular cases, azadiboriridines of type2are either isolated or proven as intermediates on the way from1to3. The three‐membered ring of the known azadiboriridines2i,m(R/R'/R” =tBu/iPr/tBu,tBu/tBu/tBu) is expanded to the five‐membered ring of the corresponding azadiborolines4i,mby the reaction with 3‐hexyne. The products4i,mare reduced to the dilithium azadiborolinates5i,mby the action of lithium; the molecular structure of acloso‐azadicarbadili‐thiaheptaborane is recognized in crystals of5i. The threemembered ring of2mis also expanded by the reaction with the iminoborane EtB ≡ NtBu giving the diazatriborolidin6m, which crystall

ISSN:0009-2940    

DOI:10.1002/cber.19911241111

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY