Peter Merbach

Zur kenntnis der chemie der metallcarbonyle und der cyanokomplexe in flüssigem ammoniak : XXXIII. Über die darstellung neuer carbamoylcarbonyl-komplexe aus bekannten und neuen kationischen carbonylverbindungen des mangans und rheniums

Abstract The covalent carbamoyl carbonyl compounds Re(CO) 5 COHN 2 , cis -M(CO) 4 (L)CONH 2 , M(CO) 3 (L) 2 CONH 2 and M(CO) 3 (D)CONH 2 (M = Mn, Re; L = PPh 3 , PEt 3 ; D = bipy, phen) are formed by reactions of the cationic complexes [Re(CO) 6 ] + , [M(CO) 5 L] + , [M(CO) 4 L 2 ] + and [M(CO) 4 D] + (M = Mn, Re; L = PPh 3 , PEt 3 ; D = bipy, phen) with liquid NH 3 with concomitant deprotonation: [M(CO) 6− n L n ] + + 2 NH 3 → M(CO) 5− n L n CONH 2 + NH 4 + ( n = 0, 1, 2) and [M(CO) 4 D] + + 2 NH 3 → M(CO) 3 (D)CONH 2 + NH 4 + The stability of the above-mentioned carbamoyl carbonyl complexes increases from the penta- to the tetra- to the tri-carbonyl derivatives. In all cases the rhenium compounds are much more stable than the corresponding manganese complexes. Whereas the carbamoyl compound Re(CO) 4 (PEt 3 )CONH 2 can be isolated by reaction of [Re(CO) 5 PEt 3 ] + with NH 3 , the corresponding manganese complex undergoes Hofmann degradation of amides even at −70°C to form HMn(CO) 4 PEt 3 and NH 4 NCO. The IR and some mass and 1 H NMR spectra of the new hexacoordinated carbamoyl carbonyl complexes are discussed and the reactions of these compounds with liquid NH 3 , HCl and CH 3 OH are described.

η3-allyl-monocyano-tricarbonylmetallate und η3-allyl-monoisonitril-tricarbonyle des mangans und rheniums

Abstract The reactions of η3-C3H4RM(CO)4 (η3-C3H5 = allyl for R = H; η3-C4H7 = 2-methylallyl for R = Me; M = Mn, Re) with NaN(SiMe3)2 lead to the formation of the η3-allylmonocyanotricarbonyl metalates [η3-C3H4RM(CO)3CN]− which can be converted into the corresponding isonitrile derivatives η3-C3H4RM(CO)3CNMe or η3-C3H4RM(CO)3CNSnMe3 by treatment with [Me3O]BF4, MeI or Me3SnCl. The new complexes are characterized by their IR and 1H NMR spectra, and in the case of the isonitrile compounds also by their mass spectra.

Zur kenntnis der cyclopentadienyl-nitrosyl-carbonyl-isonitril-komplexe der VI. Und der cyclopentadienyl-dicarbonyl-isonitril-komplexe der VII. Nebengruppe

Abstract The nitrosylcarbonylisonitrile complexes η5-C5H5M(NO)(CO)CNR (R = Me for Cr, Mo, W; R = Et, SiMe3, GeMe3, SnMe3 for Mo) are formed by treatment of the nitrosylcarbonylcyanometalates Na[η5-C5H5M(NO)(CO)CN] with [R3O]BF4 (R = Me, Et), Me3SiCl, Me3GeCl or Me3SnCl. The isoelectronic dicarbonylisonitrile compounds η5-C5H5Mn(CO)2CNR (R = SiMe3, GeMe3, SnMe3, PPh2, AsMe2) and η5-C5H5Re(CO)2CNAsMe2 are obtained by analogous reactions of Na[η5-C5H5M(CO)2CN] (M = Mn, Re) with Me3ECl (E = Si, Ge, Sn), Ph2PCl and Me2AsBr. With phosgene the anionic complexes Na[η5-C5H5M(CO)2CN] (M = Mn, Re) can be transformed into the new carbonyldiisocyanide-bridged dinuclear complexes η5-C5H5M(CO)2CN-C(O)-NC(OC)2M-η5-C5H5. Finally, the reactions of η5-C5H5M(NO)(CO)CNMe (M = Cr, Mo, W) with NOPF6, leading to the cationic dinitrosylisonitrile complexes [η5-C5H5M(NO)2CNMe]+, are described.

Chemie polyfunktioneller Liganden, 53 [1] Über methyl-substituierte Triarsa-trioxa-, Triarsa-trithiaund Triarsa-triaza-adamantane und über den stark aufgeweiteten Adamantan-Käfig im Schwefel-Derivat / Chemistry of Polyfunctional Ligands, 53 [1] About Methyl-substituted Triarsa-trioxa-, Triarsa-trithia- and Triarsa-triaza-adamantanes and about the Strongly Spread Adamantane Cage in the Sulfur Derivative

Abstract The reaction of l,l,l-tris(diiodarsinomethyl)ethane, CH3C(CH2Asl2)3 (1), with H2O, H2S and CH3NH2 in THF gives the adamantane cage compounds CH3C(CH2ASO)3 (4), CH3C(CH2ASS)3 (5) and CH3C(CH2ASNCH3)3 (6) in high yields. The crystal structure of 5 has been determinated by X-ray diffraction. The unit cell (space group P2i/w) contains 4 isolated molecules in a cubic closest packing. The heteroadamantane 5 has an enlarged cage structure with extremely spread C-C(H2)-As bond angles of 124° at the methylene carbon atoms. Some pharmacological properties of the adamantane derivatives 4 and 5 have been studied. All compounds have been characterized by mass spectrometry and infrared, Raman and X H NMR spectroscopy.

Zur Kenntnis der Chemie der Metallcarbonyle und der Cyano-Komplexe in flüssigem ammoniak : XL. Über die Reaktion kationischer Cyclopentadienyl-carbonyl-nitrosyl-Komplexe des Mangans und Rheniums mit flüssigem Ammoniak

Abstract The reactions of the cationic complexes [CpMn(CO) 2 NO] + , [MeCpMn(CO) 2 NO] + (Cp = η 5 -C 5 H 5 , MeCp = η 5 -C 5 H 4 CH 3 ), [CpRe(CO) 2 NO] + , [CpMn(CO)(L)NO] + (L = PPh 3 , PEt 2 Ph, AsPh 3 , CNMe, CNEt), {[CpMn(CO)NO] 2 Me 2 PC 2 H 4 PMe 2 } 2+ and {CpMn(CO)NO] 2 Ph 2 PC 2 H 4 PPh 2 } 2+ with liquid NH 3 yield the neutral carbamoyl complexes CpMn(CO)(NO)CONH 2 , MeCpMn(CO)(NO)CONH 2 , CpRe(CO)(NO)CONH 2 , CpMn(L)(NO)CONH 2 (L = PPh 3 , PEt 2 Ph, AsPh 3 , CNMe, CNEt), [CpMn(NO)CONH 2 ] 2 Me 2 PC 2 H 4 PMe 2 and [CpMn(NO)CONH 2 ] 2 Ph 2 PC 2 H 4 PPh 2 . Properties and reactions of these new compounds are described.

Über neue zweikernige Metallcarbonylkomplexe mit Cyclohexadienyl-cycloheptatrien-und Cyclohexadienyl-isonitril-Brücken/On New Dinuclear Metal Carbonyl Complexes with Cyclohexadienyl Cycloheptatriene and Cyclohexadienyl Isonitrile Bridges

Abstract The reactions of the electrophilic [C6H7Fe(CO)3]+ -and [C6H7Fe(CO)2CNEt]+-cations with theextremely nucleophilic [C7H7Fe(CO)3]- -anion lead to the formation of the dinuclear cyclohexadienyl cycloheptatriene bridged complexes (OC)3FeC6H7-C7H7Fe(CO)3 and EtNC(OC)2FeC6H7-C7H7Fe(CO)3. In a similar reaction the tricarbonyl cation [CeH7Fe(CO)3]+ with [Cr(CO)5CN] _ yields the dinuclear cyclohexadienyl isonitrile bridged compound (OC)3FeC6H7-NCCr(CO)5. The mass, IR and NMR data of the new complexes are reported.

Massenspektroskopishce untersuchungen an olefin-isonitril-eisendicarbonyl-komplexen

Abstract The mass spectra of the isonitrile complexes oleneFe(CO)2CNL (olene, see Table 1, L = Me, Et, SiMe3, SnMe3) are summarized and a comparative discussion is given. Whilst the successive loss of CO and the elimination of the intact isonitrile or olefin ligands are similar processes for all compounds, there are important differences in the fragmentations of the complexes olefin ligands, which are therefore noteworthy.

Zur Reaktivität von Natrium-bis-trimethylsilylamid gegenüber Metallcarbonylkomplexen mit Metall-Metall-Bindungen, I ER2-verbrückte Dicyano- und Diisonitril-octacarbonyl-dimanganate (E = Sn, Pb) / The Reactivity of Sodium Bis-trimethylsilylamide against Metal Carbonyl Complexes with Metal Metal Bonds, I ER2 Bridged Dicyano or Diisonitrile Octacarbonyl Dim anganates (E = Sn, Pb)

Abstract EPh2 bridged dicyano octacarbonyl dimetalates {Ph2E[Mn(CO)4CN]2}2- are formed by the reaction of bis(carbonyl-metalates) of tin and lead Ph2E[Mn(CO)5]2 with NaN(SiMe3)2. The new dicyano anions can be transformed with trialkyloxonium tetrafluoroborates [R′3O]BF4 or chlor-trimethylsilane and -germane into the corresponding diisonitrile complexes Ph2E[Mn(CO)4CNR′]2 (R′=Me, Et, SiMe3, GeMe3). In the case of Ph2E [Mn(CO)4CNR′]2 (R′=Me, Et; E=Sn, Pb) the two phenyl groups can be removed with dry hydrogenchloride to give Cl2E[Mn(CO)4CNR′]2.NMR and mass spectra are discussed. The vibrational spectra of the new compounds show cis-coordination of the Sn atoms and the cyano or isonitrile ligands in the carbonylmetalate fragments. This is confirmed by the X-ray structure analysis of Ph2Sn[Mn(CO)4CNMe]2 (space group P21/n).

Über die Darstellung und Eigenschaften neuer Chloro-tris(carbonylmetaIIato)-zinn(IV)-Komplexe und die Kristallstruktur von ClSn[Fe(CO)2Cp]2[Co(CO)4]. Synthesis and Properties of New Chloro Tris(carbonylmetalato) Tin(IV) Complexes and the X-ray Structure Analysis of ClSn[Fe(CO)2Cp]2[Co(CO)4]

The chloro-tris(carbonylmetalato)tin(IV) compounds, listed in Table I, are obtained by the reaction of TlCo(CO)4 or Tl[Mn(CO)5]3 with the dichloro(carbonylmetalato)tin(IV) complexes Cl2Sn[M(CO)5]2 (M = Mn, Re), Cl2Sn[Fe(CO)2Cp]2, Cl2Sn[Cr(CO)3Cp][Mn(CO)5] and Cl2Sn[Cr(CO)3Cp][Fe(CO)2Cp] in the molar ratio 1:1. Chloro-tris(carbonylmetalato)- tin(TV) compounds of the same type are also formed by treatment of TlCo(CO)4 with the trichloro(carbonylmetalato)tin(IV) complexes in the molar ratio 2 : 1. The new compounds are characterized by their analyses, mass, IR and FIR spectra. The X-ray analysis of ClSn[Fe(CO)2Cp]2[Co(CO)4] (space group P21/c) confirms the presence of 3 carbonyl - metalato groups attached to tin.

Beiträge zur Chemie der Carbonylkomplexe mit Germanium-bzw. Zinn-Übergangsmetall-Bindungen/ Contributions to the Chemistry of Carbonyl Complexes with Germanium or Tin Transition Metal Bonds

Abstract Dihalogeno bis(carbonylm etalato) germanium (IV) and tin(IV ) com pounds listed in Table I are obtained in high yields by the reaction o f TlCo(CO)4 or TlFe(CO)3NO with trihalogeno carbonylmetalato germanium(IV) and tin(IV) complexes. The new com pounds are characterized by their analyses, mass and vibrational spectra.