Synthesis of cationic germyleneiron complexes and X-ray structure of [Cp(CO)2Fe=GeMe2•DMAP]BPh4•CH3CN (Cp = C5Me5, DMAP equals 4-(dimethylamino)pyridine)

被引：28

作者：

Tobita, H ^{[1
]}

Ishiyama, K ^{[1
]}

Kawano, Y ^{[1
]}

Inomata, S ^{[1
]}

Ogino, H ^{[1
]}

机构：

[1] Tohoku Univ, Grad Sch Sci, Dept Chem, Sendai, Miyagi 98077, Japan

来源：

ORGANOMETALLICS | 1998年 / 17卷 / 05期

关键词：

D O I：

10.1021/om970870y

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Chlorogermyliron complexes Cp*(CO)(2)FeGeMe2Cl (1) and Cp*(CO)(PPh3)FeGeMe2Cl (2) undergo chloride abstraction by AgBPh4 in the presence of 4-(dimethylamino)pyridine (DMAP) to afford cationic germylene complexes [Cp*(CO)(2)Fe=GeMe2 . DMAP]BPh4 (3) and [Cp*(CO)(PPh3)Fe=GeMe2 . DMAP]BPh4 (4), respectively. Structural determination by X-ray crystallography of 1 and 3 . CH3CN revealed that both complexes have a gauche conformation with respect to the Fe-Ge bonds. The short Fe-Ge bond (2.329(3) Angstrom) and very long Ge-N (DMAP) bond (1.989(8) Angstrom) in 3 . CH3CN demonstrate the unsaturated bond character of the former and the dative bond character of the latter. The complexes 3 and 4 in dichloromethane revert to the parent complexes 1 and 2, respectively, via an electron-transfer process from the counteranion, BPh4-, followed by chlorine abstraction from the solvent.

引用

页码：789 / 794

页数：6

共 43 条

[1] OXIDATION OF TETRAPHENYLBORATE BY HEXACHLOROIRIDATE(IV) [J].

ABLEY, P ;

HALPERN, J .

JOURNAL OF THE CHEMICAL SOCIETY D-CHEMICAL COMMUNICATIONS, 1971, (20) :1238-&

[2] STRUCTURAL AND DYNAMICAL PROPERTIES OF MU-DIMETHYLGERMYL-MU-CARBONYL-DICYCLOPENTADIENYLDICARBONYLDIIRON [J].

ADAMS, RD ;

BRICE, MD ;

COTTON, FA .

INORGANIC CHEMISTRY, 1974, 13 (05) :1080-1085

[3] SPIN TRAPPING IN ELECTROCHEMISTRY .1. ELECTROOXIDATION OF ORGANO-BORIDES [J].

BANCROFT, EE ;

BLOUNT, HN ;

JANZEN, EG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (13) :3692-3694

[4] THE 1ST EVIDENCE FOR REDUCTIVE COUPLING OF TRANSITION-METAL SUBSTITUTED HALOGERMANES [J].

BARSUASKAS, G ;

LEI, D ;

HAMPDENSMITH, MJ ;

DUESLER, EN .

POLYHEDRON, 1990, 9 (05) :773-776

[5] SYNTHESIS OF CATIONIC ALKYL BIS(CYCLOPENTADIENYL)TITANIUM COMPLEXES BY ONE-ELECTRON OXIDATION OF TITANIUM(III) ALKYLS - THE STRUCTURE OF [CP2STARTIME(THF)]BPH4 AND [CP2STARTI(OH)(H2O)]BPH4.2THF [J].

BOCHMANN, M ;

JAGGAR, AJ ;

WILSON, LM ;

HURSTHOUSE, MB ;

MOTEVALLI, M .

POLYHEDRON, 1989, 8 (13-14) :1838-1843

[6] PREPARATION AND STRUCTURE OF GERMANIUM-BRIDGED IRON CARBONYL COMPLEX [(CH3)2GE]3FE2(CO)6 [J].

BROOKS, EH ;

ELDER, M ;

GRAHAM, WAG ;

HALL, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1968, 90 (13) :3587-&

[7] STRUCTURE OF THE REACTION-PRODUCT OF PENTAPHENYLGERMOLE AND DIIRON ENNEACARBONYL - MU-(1-(1,2,3,4-TETRAPHENYLBUTADIENYL)PHENYLGERMYLENE)-OCTACARBONYLDIIRON(FE-FE) [J].

CURTIS, MD ;

BUTLER, WM ;

SCIBELLI, J .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1980, 192 (02) :209-218

[8] CRYSTAL-STRUCTURE OF A 5-MEMBERED COBALT-GERMANIUM-IRON HETEROCYCLE, ((PI-C5H5)CO(CO))2(GECL2)2FE(CO)4 [J].

ELDER, M ;

HUTCHEON, WL .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1972, (02) :175-&

[9] CRYSTAL AND MOLECULAR STRUCTURE OF TRI-MU-DIMETHYLGERMANIUM-BIS(TRICARBONYLIRON) [J].

ELDER, M ;

HALL, D .

INORGANIC CHEMISTRY, 1969, 8 (07) :1424-&

[10] CRYSTAL AND MOLECULAR STRUCTURE OF MU-CARBONYL-BIS-MU-DIPHENYLGERMANIUM-BIS(TRICARBONYLIRON), [GE(C6H5)2]2FE2(CO)7 [J].

ELDER, M .

INORGANIC CHEMISTRY, 1969, 8 (12) :2703-&

← 1 2 3 4 5 →

Synthesis of cationic germyleneiron complexes and X-ray structure of [Cp*(CO)2Fe=GeMe2•DMAP]BPh4•CH3CN (Cp* = C5Me5, DMAP equals 4-(dimethylamino)pyridine)

Synthesis of cationic germyleneiron complexes and X-ray structure of [Cp(CO)2Fe=GeMe2•DMAP]BPh4•CH3CN (Cp = C5Me5, DMAP equals 4-(dimethylamino)pyridine)