Heidi I. Hayen

Darstellung, charakterisierung und reaktivität der metallcyclischen alkenylketon-komplexe Cp*(CO)2Cr[R1CCR2C(O)Me] (Cp* = η5-C5Me5; R1, R2 = H. Me, Ph, CH2OH, (CH2)2Me, (CH2)5Me)

The photoinduced reaction of Cp*Cr(CO)3Me (Cp* = η5-C5Me5) and alkynes R1CCR2 (R1, R2 = H, Me, Ph, CH2OH, (CH2)2Me, (CH2)5Me) yields the metallacyclic alkenylketone complexes Cp*(CO)2Cr[R1CCR2C(O)Me] and the isomers Cp*(CO)2Cr[R2CCR1C(O)Me] (II). Complexes II show high reactivity: they react with PMe3 yielding the CO substitution products Cp*(CO)(PMe3)Cr[R1CCR2C(O)Me] (R1 = H; R2 = H, Ph) as well as the ylidic metallacyclopropane adduct Cp*(CO)2Cr[(PMe3)HCCHCOMe]. The reaction of Cp*(CO)2Cr[HCCHC(O)Me] with NO gives Cp*Cr(NO)2NO2; with ClNO the products formed are Cp*Cr(NO)2Cl and [Cp*Cr(NO)Cl]2. Complexes II and CF3COOH or HCl gas release the free alkenylketone R1HCCR2COMe and the paramagnetic products Cp*Cr(CF3COO)2 and [Cp*CrCl2]2. Photolysis of II in CHCl3 yields [Cp*CrCl2]2, H2R1CCR2HCOMe and Cl2CCHCl.

Unerwartete fragmentierungs-, nitrosylierungs- und hydrierungsreaktionen bei der umsetzung der metallacyclischen alkenylketonkomplexe

Summary The metallacyclic alkenylketone complexes react with NO, ClNO and CF 3 COOH, forming unexpected complexes in all cases. Under fragmentation of the alkenylketone ligand Ia and NO yield the acetylene oxo complexes C 5 H 5 W(O)(C 2 H 2 )Me and C 5 H 5 W(O)(C 2 H 2 )COMe. The oxygen for the oxo ligands derives from nitric oxide. The reaction of Ia and ClNO leads to elimination of the alkenylketone ligand, uptake of CO and formation of the known dimeric complex [C 5 H 5 W(CO) 3 ] 2 on the one hand, and to conversion of the η 2 -bonded alkenylketone ligand to an η 1 -bonded alkenyl ligand yielding C 5 H 5 (NO) 2 W(η 1 -CH CHCOMe) on the other. The C 5 Me 5 , derivative Ib and ClNO, however, form exclusively the metallacyclic nitrosylchloro complex . Complexes Ia and Ib react with CF 3 COOH and give Cp′(CO)(CF 3 OO) 2 W(η 1 -CH 2 CH 2 COMe). In this reaction the alkenyl double bond of Ia and Ib is hydrogenated and one CO ligand is substituted by two CF 3 COO groups that occupy trans positions in a tetragonal pyramid.

Ein- und zweikernige Ferrocenophane mit aromatischen Thioester-Brücken

Abstract Sulphur-containing ferrocenophanes containing one or two ferrocene units were prepared using either ferrocene-1,1′-dithiol, Fe(C5H4SH)2, or ferrocene-1,1′-bis(carbonylchloride), Fe(C5H4COCl)2, as starting materials. Ferrocene-1,1′-dithiol reacts with phthaloyl chloride in an unexpected manner to give 1,3-dithia-(2-phthalido)-[3]ferrocneophane. The structures of the new compounds can be deduced from their 1H and 13C NMR spectra.

Umsetzungen des asymmetrischen, zweikernigen Dioxokomplexes C5Me5(CO)3WW(O)2C5Me5 mit Cl2, Br2, I2, HCl, CF3COOH, NOCl, NO und Luft. Molekülstruktur von C5Me5W(CO)2Br3

Abstract The dinuclear dioxo complex C 5 Me 5 (CO) 3 WW(O) 2 C 2 Me 5 ( 1 ) reacts with Cl 2 or NOCl, Br 2 , I 2 to afford the trihalo complexes C 5 Me 5 W(CO) 2 X 3 (X = Cl, Br, I), and the dioxohalo complexes (C 5 Me 5 W(O) 2 X. HCl and 1 react to give the dimeric complex [C 5 Me 5 W(CO) 2 Cl] 2 whereas CF 3 COOH and 1 give the μ-uxo complex [C 5 Me 5 W(CO)(CF 3 COO)] 2 O. NO or air oxidizes 1 to the dinuclear [C 5 Me 5 W(O) 2 ] 2 O. The crystal structure of C 5 Me 5 W(CO) 2 Br 3 has been determined by X-ray diffraction.

Darstellung, Charakterisierung und Molekülstruktur des η2-Acylkomplexes C5Me5(CO)(CF3COO)2W[η2-C(O)CH2CH2COMe]

Abstract The reaction of the five-membered metallacyclic alkenylketone complex C5Me5(CO)2 W[HC=CHC(O) )Me (I) with CF3COOH yields the η2-acyl complex C5Me5(CO(CF3COO)2 W[η 2 -C(O )CH2CH2COMe] (II). Compound II was identified from elemental analysis, by IR, 1H, 13F NMR spectroscopy and X-ray diffraction analysis. Thermolysis of II leads to elimination of one CO and formation of the alkyl complex cis-C5Me5(CO)(CF3COO)2W(CH2CH2COMe) (III). The reaction of II with HCl gives the substitution product C5Me5(CO)(Cl)2 W[η 2 C(O ))CH2CH2COMe] (IV).

Darstellung neuer trimethylphosphonium-salze und eines trifluoressigsäure-komplexes durch umsetzung der ylidischen metallacyclopropan-komplexe Cp′(CO)(L)W[(PMe3)HCCHCOMe] (Cp′ = η5-C5H5, η5-C5Me5; L = CO, PMe3) mit CF3COOH. Reaktionen von [C5Me5W(CO)2(CF3COO)2][PMe3CH2CH2COMe] mit CO, PMe3, NOBF4 und Et3OBF4

Abstract The reaction of ylidic metallacyclopropane complexes Cp′(CO) 2 W[(PMe 3 )HCC HCOMe] (Cp′ = η 5 -C 5 H 5 , η 5 -C 5 Me 5 ) with CF 3 COOH results in an opening of both metal-carbon σ bonds, and the formation of the trimethylphosphonium salts [Cp′W(CO) 2 (CF 3 COO) 2 ][PMe 3 CH 2 CH 2 COMe]. When this reaction is carried out with the PMe 3 derivative Cp(CO)(PMe 3 ) W[(PMe 3 )HCC HCOMe], the electron density of the metal is of such a magnitude that one CF 3 COO ligand of the intermediate anion [CpW(CO)(PMe 3 )(CF 3 COO) 2 ] − is protonated, thus yielding the neutral trifluoracetic acid complex CpW(CO)(PMe 3 )(CF 3 COO)(CF 3 COOH). Spectroscopic results indicate that the CF 3 COOH ligand is coordinated to the metal through a free electron-pair located on the OH function. The ylidic metallacyclopropane complex CpW(CO)(PMe 3 ) W[(PMe 3 )HCC HCOMe] forms the five-membered metallacycle Cp(CO)(PMe 3 ) W[HCCHC(O )Me] under CO 2 pressure releasing the ylidic PMe 3 substituent. Reaction of the salt [C 5 Me 5 W(CO) 2 (CF 3 COO) 2 ][PMe 3 CH 2 CH 2 COMe] with CO, PMe 3 , NOBF 4 , and Et 3 OBF 4 affords the neutral complexes C 5 Me 5 W(CO) 3 (CF 3 COO), C 5 Me 5 W(CO) 2 (PMe 3 (CF 3 COO), C 5 Me 5 W(CO)(PMe 3 ) 2 (CF 3 COO), C 5 Me 5 W(NO) 2 (CF 3 COO), and C 5 Me 5 W(CO)(CF 3 COO) 2 Et, respectively. Every one of the novel compounds is characterized by IR and NMR spectroscopy.

Reaktionen der substituierten metallacyclischen Alkenylketon-Komplexe Cp*(CO)2M[R1CCR2C(O)Me] (M = Cr, Mo, W; Cp* = η5-C5Me5; R1, R2 = H, Me,Ph) mit Stickstoffmonoxid und Nitrosylchlorid

Depending on the metal and the substituents R1 and R2, each of the metallacyclic alkenylketone complexes Cp*(CO)2M[R1C. The chromacycles Cp*(CO)1Cr[R1CCR2C(O)Me] (Ia: R1 = H, R2 = Ph; Ila: R1 = R2 = Me) and nitric oxide give r The tungstenacycle Cp*(CO)2W[PhCCHC(O)Me] (Ic) reacts with NO to give analogous Cp*W(NO)2(η1-PhCCHCOMe) (IVc). The reaction of the chromacycles Ia and IIa with nitrosyl chloride leads only to chloro complexes such as Cp*Cr(NO)2Cl (v), [Cp*Cr(NO)Cl]2 (VI) molybdena- and tungstenKacycles during the reaction with ClNO. Complex Cp*(CO)2Mo[MeCCMeC(O)Me] (IIb) reacts with nitrosyl chloride to give Cp*(CO)Cl2Mo[MeCCMeC(O)Me] (x) and [Cp*M The phenylsubstituted complex Cp*(CO)2W[PhCCHC(O)Me] (Ic), however, gives Cp* (CO)Cl2W[PhCCHC(O)Me] (IX).

Preparation and crystal structure of the dinuclear, asymmetric dioxo complex (η5-C5Me5)(CO)3W–W(O)2(η5-C5Me5)

The dinuclear, asymmetric, dioxo complex (η5-C5Me5)(CO)3W–W(O)2(η5-C5Me5)(3) can be prepared by air oxidation of [(C5Me5)W(CO)2]2(1) or (C5Me5)W(CO)2(µ-H)]2(2); in this compound WI is directly connected with WV.