Übergangsmetall-Carbin-Komplexe, LX [1]. Neue Triphenylsilyl-Carben-Komplexe des Rheniums durch Umsetzung eines kationischen Carbinkomplexes mit Nucleophilen / Transition Metal Carbyne Complexes, LX [1] Novel Triphenylsilyl Carbene Complexes of Rhenium by Reaction of a Cationic Carbyne Complex with Nucleophiles

1980 ◽  
Vol 35 (9) ◽  
pp. 1083-1087 ◽  
Author(s):  
Ernst Otto Fischer ◽  
Paul Rustemeyer ◽  
Dietmar Neugebauer

The reaction between C5H5Re(CO)3 and LiSi(C6H5)3 affords the compound C5H5(CO)2ReC(OCH3)Si(C6H5)3 after subsequent alkylation with CH3SO3F. This complex reacts with BF3 to yield [C5H5(CO)2ReCSi(C6H5)3]BF4. This cationic carbyne complex yields C5H5(CO)2ReC(CH1)Si(C6H5)3 with LiCH3 and C5H5(CO)2ReC(H)Si(C6H5)3 with (C4H9)4NBH4. Reaction conditions, properties and spectroscopic data of the new com­pounds as well as an X-ray structure determination of C5H5(CO)2ReC(H)Si(C6H5)3 are reported.

1982 ◽  
Vol 37 (10) ◽  
pp. 1274-1278 ◽  
Author(s):  
Werner Roll ◽  
Ernst Otto Fischer ◽  
Dietmar Neugebauer ◽  
Ulrich Schubert

The reaction of trans-bromotetracarbonyl(phenylcarbyne)chromium (1) with lithium phenylselenolate and subsequent protonation with aqueous hydrochloric acid leads to (CO)5Cr[Se2(C6H5)2] (3) and (CO)4Cr(μ-SeC6H5)2Cr(CO)4 (4). From 1 and lithium 4-methylphenylthiolate (CO)5CrC(C6H5)SC6H4CH3 (5) and (CO)5CrS(C2H5)(4-CH3C6H4) (6) are obtained, if triethyloxonium tetrafluoroborate is used instead of hydrochloric acid. The analoguous reaction of 1 with lithium phenylselenolate yields the seleno ether complex (7). Reaction conditions, properties, spectroscopic data and the results of an X-ray structure determination of the binuclear complex (4) are reported.


1984 ◽  
Vol 39 (5) ◽  
pp. 668-674 ◽  
Author(s):  
Ernst Otto Fischer ◽  
Rudolf Reitmeier ◽  
Klaus Ackermann

The hexacarbonyl compounds of chromium, molybdenum and tungsten react with the highly nucleophilic agent Li NiPr2 and in a subsequent alkylation with (Et3O)BF4 to give the carbene complexes (CO)5M[C(N′Pr2)OEt] (1, 3, 4). In case of W(CO)6 and Mo(CO)6 the novel biscarbene complexes cis(CO)4M[C(NiPr2)OEt]2 (2, 5) are additionally obtained. Reaction conditions, properties and spectroscopic data of the new compounds are reported. The molecular structure of cis(CO)4W[C(NiPr2)OEt]2 (4) was determined by X-ray crystallography


1992 ◽  
Vol 47 (5) ◽  
pp. 645-655 ◽  
Author(s):  
D. Sellmann ◽  
H. Schillinger ◽  
F. Knoch

Ni(II) salts and the tetradentate thioether-thiolate ligand ′S4-C2′2- (= 1,2-bis(2-mercaptophenylthio)ethane(2-)) yield [Ni(′S4-C2′)]x (1), that also forms when Na2[Ni(′S2′ )2] (′S22-′ = o-benzenedithiolate(2-)) is alkylated by 1,2-dibromoethane. In boiling pyridine 1 adds two solvent molecules and gives pseudooctahedral [Ni(pyr)2(′S4-C2′ )] (2) which was characterized by X-ray structure determination. Reaction of 1 with PMe3 yields [Ni(PMe3)(′S4-C2′)] (4). X-ray structure determination of 4 showed that the Ni center is surrounded by one P and four S atoms in a distorted tetragonal pyramid in which the P atom, one thioether S atom and both of the thiolate S atoms form the base while the second thioether S atom occupies the apical position. Reaction of 1 with n-BuLi leads to removal of the C2H4 bridge of the ′S4-C2′2- ligand and formation of Li2[Ni(′S2′)2].When [Ni(acac)2]3 is reacted with ′buS4-C2′2 (= 1,2-bis(3,5-ditertiarybutyl-2-mercaptophenylthio)ethane(2-)) which is analogous to ′S4-C2′2-, the trinuclear [Ni(′buS4-C2′)]3 (3) forms. 3 · THF was characterized by X-ray structure determination. It contains one tetrahedrally distorted and two planar [NiS4] cores that are connected via the C2H4 groups of the ligands such that a macrocycle forms. PMe3 cleaves 3 to give mononuclear [Ni(PMe3)(′buS4-C2′)] (5). Due to its lability, it was characterized only by spectroscopic methods.


1982 ◽  
Vol 37 (10) ◽  
pp. 1284-1288 ◽  
Author(s):  
Ernst Otto Fischer ◽  
Jiabi Chen ◽  
Ulrich Schubert

Abstract Symmetrical anhydrides of hydroxycarbene complexes of manganese and rhenium, [π-C5H5(CO)2MC(R)]2O, (M = Mn, Re) are prepared by reaction of cationic carbyne complexes [π-C5H5(CO)2MCR]BX4 with the corresponding metal carbonyl acylates Li[π-C5H5(CO)2MC(O)R]. [π-C5H5(CO)2MnC(C6H5)]2O is also obtained by controlled hydrolysis of π-C5H5(CO)2MnCX(Br)Ce6H5. The new complexes are characterized spectroscopically and by an X-ray structure analysis of [π-C5H5(CO)2MnC(C6H5)2O.


1983 ◽  
Vol 38 (1) ◽  
pp. 67-70 ◽  
Author(s):  
Werner Sieber ◽  
Mathias Wolfgruber ◽  
Dietmar Neugebauer ◽  
Olli Orama ◽  
Fritz R. Kreißl

Abstract Dicarbonyl(η5-cyclopentadienyl)(η1 -cyclopropylketenyl)(trimethylphosphane)tungsten reacts with carbon monoxide under reduction of the ketene moiety forming a (σ-bonded acetylene compound. Reaction conditions, spectroscopic data and the X-ray structure of the new compound are reported.


1985 ◽  
Vol 40 (11) ◽  
pp. 1500-1503 ◽  
Author(s):  
Werner J. Sieber ◽  
Dietmar Neugebauer ◽  
Fritz R. Kreißl

Carbonyl(η5-cyclopentadienyl)(η2-4-methylphenylketenyl)trimethylphosphinetungsten reacts with decaborane(14) under conversion of the η2-ketenyl into a η2-alkyne complex. Reaction conditions, spectroscopic data and the X-ray structure of the new compound are reported.


1987 ◽  
Vol 40 (7) ◽  
pp. 1169 ◽  
Author(s):  
JA Elix ◽  
KL Gaul ◽  
M Sterns ◽  
MW Binsamsudin

The structure determination of thiomelin (2,4-dichloro-1,8-dihydroxy-5-methoxy-6-methyl-9H-xanthen-9-one) (3), an unusual lichen metabolite probably derived biosynthetically by oxidative ring opening of a precursor anthraquinone, is reported. The crystal structure of thiomelin diacetate (4) was determined by X-ray diffraction, while that of the cogenors 8-O-methylthiomelin (5), 4-dechlorothiomelin (7), 4-dechloro-8- O- methylthiomelin (9), 2-dechloro-8- O- methylthiomelin (10) and 2,4-dichloro-l-hydroxy-7-methoxy-6,8-dimethyl-9H-xanthen-9-one (12) were deduced from spectroscopic data.


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