摘要:

Properties of Chalcogen–Chalcogen Bonds, XV1). ‐ Lithium 2,4,6‐Tri‐tert‐butylphenylselenide: Synthesis, Structure, and Reactions with Formation of Se – P, Se – C, Se – Si, Se – Sn, and Se – Au BondsBis(2,4,6‐tri‐tert‐butylphenyl)diselenide (1) is reduced by lithium triethylhydridoborate to give lithium 2,4,6‐tri‐tert‐butyl‐phenylselenide (2) in high yield.2crystallizes with three molecules of tetrahydrofuran coordinated to lithium ([2(THF)3] 2a, space groupP&1macr;Z=4). The monomeric compound2acontains four‐coordinate lithium bonded to two‐coordinate selenium.2(LiSeR) reacts with the nonmetal and metal halidestBu2PCl, CH2Cl2, Me3SiCl, Me3SnCl, and Ph3PAuCl to givetBu2PSeR (3), RSeCH2Cl (4), (RSe)2CH2(5), Me3SiSeR (6), Me3SnSeR (7), and the novel gold(I) selenophenolate derivative Ph3PAu

ISSN:0009-2940    

DOI:10.1002/cber.19911240602

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

{Bis[bis(trimethylsilyl)methyl]stannio(II)}bis(η2‐ethene)nickel(O) and Related Compounds, Part IThe reaction of Ni(C2H4)3and bis{bis(trimethylsilyl)methyl}‐stannene affords the crystalline, coordinatively unsaturated complex (C2H4)2Ni  Sn{CH(SiMe3)2}2(1). The NMR spectra of1show for the tin moiety a temperature‐dependent solvate complex formation (thf) and for the nickel moiety a hindered rotation of the ethene ligands at low temperature. X‐ray structure analysis indicates Sn – Ni multiple‐bond character. Upon addition of donor molecules to1the addition compounds (C2H4)2Ni – Sn{CH(SiMe3)2}2(donor) [donor = NH3:2a; pyridine:2b; (Me2N)3PO:2c] are obtained. According to the low‐temperature NMR spectra the complexes are asymmetric in their ground state. Similar to the formation of the adducts2a–c, the title compound1reacts with LiHAliBu3as a source of LiH in ether/tmeda to form the hydride adduct [Li(tmeda)2]+ [(C2H4)2Ni – Sn{CH(SiMe3)2}2}2(H)]ominus; (2d). Displacement of the ethene ligands in1by CO yields with conservation of the Ni – Sn bond the complex (CO)3Ni Sn{CH(SiMe3)2}2(3). From this complex the donor adducts (CO)3Ni – Sn{CH(SiMe3)2}2(donor) [donor = NH3:4a; pyridine:4b; (Me2N)3PO:4c] are prepared. For the donor‐ligand carbonyl complexes the ground state has been shown to be asymmetric

ISSN:0009-2940    

DOI:10.1002/cber.19911240603

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Photolytic and Thermic Reactions of μ3‐As[WCp(CO)2]3with Fe(CO)5and Fe2(CO)9; X‐Ray Structure Analyses of the Clusters FeW2Cp2(CO)7[μ3‐As–WCp(CO)3], Fe2WCp(CO)6H[μ3‐As–WCp(CO)3]μ3‐As[WCp(CO)2]3(1) (Cp = C5H5) reacts with Fe(CO)5photolytically and thermically to yield FeW2Cp2(CO)7[μ3‐As–WCp(CO)3] (5) and Fe2WCp(CO)8H[μ3‐As–WCp(CO)3] (6), respectively. Thermal reaction of1with Fe2(CO)9leads to the compound Fe2WCp(CO)8H[μ3‐As–FeCp(CO)2] (7besides5and6. The products have been characterized by spectroscopic m

ISSN:0009-2940    

DOI:10.1002/cber.19911240604

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

The reaction of the tetrafluorophosphoranes RPF4[R  CH3, C6H5, C6F5, (CH3)3SiCH2, and 2,5‐(CH3)2C6H3] withN,N,Ń‐trimethyl‐N′‐(trimethylsilyl))ethylenediamine (1) yields the corresponding triflurophosphoranes2–6by cleavage of the Si – N bond and elimination of (CH3)3SiF. In an analogous reaction the difluorophosphoranes R1R2PF2N(CH3)CH2CJ2N‐(CH3)2(R1 R2 C6H5,7: R1 C6H5, R2 C4H4N,8) are formed. Some of theseN,N,Ń‐trimethylethylenediamine‐substituted di‐ and trifluorophosphoranes react with PF5as a Lewis acid to form the corresponding azonium hexafluorophosphates9–12as a result of fluoride abstraction and intramolecular (CH3)2N→P donor‐acceptor interaction. Compound13shows dynamic behaviour in solution. An exchange process is observed for the axial and equatorial fluorine atoms by19F‐ and31P‐NMR spectroscopy. An X‐ray structure analysis of the compounds10–12reveals the expected trigonal‐bipyramidal geometry at phosphorus. The ethylenediamine ligand is found to form a chelate ring, whereby one axial and one equatorial site are bridged. The coor

ISSN:0009-2940    

DOI:10.1002/cber.19911240605

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

FluorothiatriazinesFrom the reaction of (ClCN)2(ClSN) (1) with AgAsF6in liquid SO2(ClCN)2(SN)⊕ AsF⊖06 (2) is obtained in quantitative yield. With CsF2gives (ClCN)2(FSN) (3), which slowly dismutates at room temperature to form (ClCN)(FCN)(FSN) (4) and1. Fluorination of 1 with SbF3yields (FCN)2(FSN) (5). With AsF55 forms the salt (FCN)2(SN)⊕AsF⊖ (6). The cation of6is transformed by NOCl or CsBr into the corresponding neutral derivatives (FCN)2(ClSN) (7) and (FCN)2(BrSN) (8), respectively. The gas‐phase structure of5was determined by electron diffraction. The influence of the different exocyclic substituents on the bond properties in this ring system is explained by means of MNDO cal

ISSN:0009-2940    

DOI:10.1002/cber.19911240606

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Synthesis and Reactions of Bis(fluorosulfinyl)difluoromethane, F2C(SOF)2From F2C(SF3)2(1) and AsF5the thermally labile monosulfonium salt F3SCF2SF2+AsF6−(2) is prepared in SO2as a solvent, while under the same conditions the corresponding tetrafluoroborate is solvolyzed to give an isomeric mixture of F2C(SOF)2(5a,b). In the reaction of5a,bwithN‐silylated amines F2C[S(O)NMe2]2(7a,b),(8a,b), and(9a,b) are formed. The structure of thecisderivative8bhas been determined by X‐ray diffraction. From5a,band HCl the rather unstable F2C[S(O)Cl]2(10a,b) is obtained, which is hydrolyzed to F2C[S(O)OH]2(1

ISSN:0009-2940    

DOI:10.1002/cber.19911240607

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

trans‐N2S2‐Macrocyclic Ligands with Pendant Carboxylic Groups. ‐ Synthesis of 6,7,8,9,15,16,17,18‐Octahydrodibenzo[f,m][1,8,4,11]dithiadiazacyclotetradecine‐8,17‐diacetic Acid (H2L1); Structures of Corresponding Copper ComplexesThe macrocyclic ligand with pendant carboxylic groups 6,7,8,9,15,16,17,18‐octahydrodibenzo[f,m][1,8,4,11]dithiadiazacyclotetradecine‐8,17‐diacetic acid (H2L1) and its Ni(II) and Cu(II) complexes, [NiL1]3(H3O·ClO4)4·H2O (1) and [Cu(HL1)]ClO4·1.5 H2O (2), have been prepared. The coordination properties of H2L1towards Ni(II) and Cu(II) in aqueous solutions are independent on the pH according to UV/Vis‐spectral measurements. The structures of2and of [CuL2]ClO4(3) with HL2= 6,7,8,9,15,16,17,18‐octahydrodibenzo[f,m][1,8,4,11]dithiadiazacyclodetradecine‐8‐acetic acid have been determined by X‐ray crystallography. In2, all six donor atoms of the ligand are coordinated, forming an octahedron. Due to their size the metal atoms are not incorporated in the ligand cavity. The ligand is folded in such a way, that the N‐donor atoms are intrans, and the S‐(and O‐)donor atoms incispositions. In3, the five donor atoms form a rather regular bipyramid with the N atoms in the axial positions. The stereochemistry of the ligan

ISSN:0009-2940    

DOI:10.1002/cber.19911240608

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Dirhenioethyne (OC)5Re–CC–Re(CO)5as Building Block for the Synthesis of Carbonyl Metal ClustersThe dimetallated ethyne (OC)5Re–CC–Re(CO)5(1) reacts with (Ph3P)2Pt(η2‐C2H4), Fe2(CO)9, and Co2(CO)8to give the acetylide‐bridged complexes PtRe2(μ3‐η1:η1:η2‐CC)(CO)9‐(PPh3)2(2), FeRe2(μ3‐μ1:η1:η2‐CC)(CO)13(3), and Co2Re2‐(μ4‐η1:η1:η2:η2‐CC)(CO)14(4), resp., whose structures have been determined by X‐ray diffraction. These reactions of (CO)5Re–CC–Re(CO)5proceed similarly to those of the isolobal

ISSN:0009-2940    

DOI:10.1002/cber.19911240609

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Ab initio quantum chemical calculations evidence a very flat potential hypersurface for folding of parent cyclotetraphosphane. This is in accord with a corresponding vibrational analysis. Electronegative substituents increase folding of the fourmembered ring system.

ISSN:0009-2940    

DOI:10.1002/cber.19911240610

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY

摘要:

Organolanthanide(II) Chemistry: Synthesis and Structure of [Cp*Sm(μ‐OC)2FeCp*]2The tetranuclear complex [Cp*Sm(μ‐OC)2FeCp*]2(3) has been prepared by reaction of Cp*2Sm(THF)2with [Cp*Fe(CO)2]2and structurally characterized by single‐crystal X‐ray di

ISSN:0009-2940    

DOI:10.1002/cber.19911240611

出版商:WILEY‐VCH Verlag    

年代:1991

数据来源: WILEY