Comparative mass spectrometric investigation of transition metal polymethylcyclopentadienylcarbonyl complexes

Lyatifov, I.R.; Gulieva, G.I.; Mysov, E. I.; Babin, V. N.; Materikova, R.B.

doi:10.1016/0022-328x(87)80124-9

Cited by 9 publications

(2 citation statements)

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“…Our instrument is not set up to go beyond that voltage, but the cracking pattern of most molecules depends only weakly on electron energy in this voltage range; experiments with the traditional 70 eV electron energy value yielded exactly the same mass spectrum. This spectrum, which matches previously reported data, 24,25 makes it immediately clear why the electron bombardment approach works in this case; it creates a number of manganese-containing highly reactive ions, species that are likely to stick to the surface upon contact with close to unit probability.…”

supporting

confidence: 88%

Activation of Metal–Organic Precursors by Electron Bombardment in the Gas Phase for Enhanced Deposition of Solid Films

Sun

Qin

Zaera

2012

J. Phys. Chem. Lett.

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The incorporation of gas-phase electron-impact ionization and activation of metal-organic compounds into atomic layer deposition (ALD) processes is reported as a way to enhance film growth with stable precursors. Specifically, it is shown here that gas-phase activation of methylcyclopentadienylmanganese tricarbonyl, MeCpMn(CO)3, which was accomplished by using a typical nude ion gauge employed in many ultrahigh-vacuum (UHV) studies, enhances its dissociative adsorption on silicon surfaces, affording the design of ALD cycles with more extensive Mn deposition and at lower temperatures. Significantly higher Mn uptakes were demonstrated by X-ray photoelectron spectroscopy (XPS) on both silicon dioxide films and on Si(100) wafers Ar(+)-sputtered to remove their native oxide layer. The effectiveness of this electron-impact activation approach in ALD is explained in terms of the cracking patterns seen in mass spectrometry for the metal-organic precursor used.

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supporting

confidence: 88%

Activation of Metal–Organic Precursors by Electron Bombardment in the Gas Phase for Enhanced Deposition of Solid Films

Sun

Qin

Zaera

2012

J. Phys. Chem. Lett.

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“…It showed the molecular ion at m / z 630 and a base peak at m / z 600 corresponding to the loss of CO and 2H. The loss of two H atoms from the C 5 Me 5 ligand in the fragmentation of Cp* complexes is well documented …”

Section: Resultsmentioning

confidence: 97%

Photochemical Reactions of the Rhenium Dinitrogen Phosphine and Phosphite Complexes Cp*Re(CO)(L)(N₂) (L = P(OMe)₃, P(OEt)₃, P(OPh)₃, P(OCH₂)₃CCH₃, PPh₃) in Hydrocarbon Solvents

Leiva

Sutton

1998

Organometallics

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Results are reported for the UV photolysis of the rhenium dinitrogen phosphite and phosphine complexes Cp*Re(CO)(L)(N2) (L = P(OEt)3 (1), P(OPh)3 (2), P(OCH2)3CCH3 (3), P(OMe)3 (4), PPh3 (5)) in hydrocarbon solvents. Irradiation of 1 in hexane yielded cis and trans isomers of the cyclometalated complex Cp*Re(CO){η2-P(OCH2CH2)(OEt)2}H (6) and a third product identified as agostic -6, in which a methyl C−H bond of one of the ethoxy groups forms an agostic interaction with the metal. This complex decayed to give the other two isomers of 6 over time. Irradiation of 1 in benzene afforded the above compounds plus two isomers of a benzene C−H activation product Cp*Re(CO){P(OEt)3}(Ph)H (7). The latter isomers and the agostic complex all decayed over time to leave only the cis and trans isomers of 6. The final observed ratio of cis(P,H)- 6 to trans(P,H)- 6 was 76:24. Irradiation of 2 in hexane, cyclohexane, or benzene produced no evidence of any intermolecular C−H activation product. In each case, two products resulted, one of which was the cis(P,H) isomer of the orthometalated complex Cp*Re(CO){η2-P(OC6H4)(OPh)2}H (8) and the other of which was the agostic complex agostic- 8, which slowly decayed away in favor of cis(P,H)- 8. In a similar way, the triphenylphosphine complex 5 gave no observable benzene C−H activation product, and agostic and cis isomers of the intramolecular complex 11 were formed. These results indicate an overwhelming thermodynamic preference for cyclometalation over intermolecular C−H activation with these phosphorus ligands. The cage phosphite complex 3, for which cyclometalation is hindered, gave an observable, but unstable, benzene C−H activation product 9 on irradiation in this solvent but no identifiable products when irradiated in hexane or cyclohexane. The product from irradiation of the trimethyl phosphite complex 4 in benzene, cyclohexane, or hexane is completely different from any of the above and does not result from C−H activation. It is formulated as the binuclear phosphonate complex [Cp*Re(CO){PO(OMe)2}(CH3)]2 (10) involving methyl migration from a trimethyl phosphite ligand to the metal.

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Halbsandwichkomplexe des Iridiums mit Tetramethylcyclopentadienyl als Ringligand

Mahr

Nürnberg

Werner

2003

Zeitschrift anorg allge chemie

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Die Iridium(I)‐Komplexe [(η5‐C5HMe4)Ir(C2H4)2] (2) und [(η5‐C5HMe4)Ir(CO)2] (4), die aus [IrCl(C2H4)2]2 bzw. [IrCl(CO)3]n und LiC5HMe4 dargestellt werden können, reagieren sowohl mit Tosylchlorid als auch mit Halogenen X2 (X = Cl, Br, I) unter oxidativer Addition zu entsprechenden Iridium(III)‐Verbindungen. Bei Einwirkung von CO oder PR3 auf die Komplexe [(η5‐C5HMe4)IrX2]n (7—9) findet eine Spaltung der Halogeno‐Brückenbindungen statt, und es entstehen die einkernigen Produkte [(η5‐C5HMe4)IrX2(CO)] (10, 11) und [(η5‐C5HMe4)IrX2(PR3)] (12—20). Die Molekülstruktur von [(η5‐C5HMe4)IrBr2(PiPr3)] (18) wurde kristallographisch bestimmt. Bei den Umsetzungen von 8 (X = Br) und 9 (X = I) mit Ph2P(CH2)nPPh2 (n = 1 oder 2) bilden sich die verbrückten Verbindungen [{(η5‐C5HMe4)IrX2}2{μ‐Ph2P(CH2)nPPh2}] (21—23). Die Dihalogenokomplexe [(η5‐C5HMe4)IrI2(PPh3)] (16) und [(η5‐C5HMe4)IrX2(PiPr3)] (17—19) reagieren mit Hydridreagenzien zu den Dihydrido‐ bzw. Monohydrido‐Derivaten [(η5‐C5HMe4)IrH2(PPh3)] (24) bzw. [(η5‐C5HMe4)IrH(X)(PiPr3)] (25—27). Die ähnlichen Dimethyl‐ und Monomethyl‐Verbindungen [(η5‐C5HMe4)Ir(CH3)2(PiPr3)] (28) und [(η5‐C5HMe4)IrCH3(I)(PiPr3)] (29) sind aus den Dihalogeno‐Vorstufen 18 bzw. 19 und CH3MgI im Molverhältnis 1:2 bzw. 1:1 erhältlich.

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Comparative mass spectrometric investigation of transition metal polymethylcyclopentadienylcarbonyl complexes

Cited by 9 publications

References 9 publications

Activation of Metal–Organic Precursors by Electron Bombardment in the Gas Phase for Enhanced Deposition of Solid Films

Activation of Metal–Organic Precursors by Electron Bombardment in the Gas Phase for Enhanced Deposition of Solid Films

Photochemical Reactions of the Rhenium Dinitrogen Phosphine and Phosphite Complexes Cp*Re(CO)(L)(N₂) (L = P(OMe)₃, P(OEt)₃, P(OPh)₃, P(OCH₂)₃CCH₃, PPh₃) in Hydrocarbon Solvents

Halbsandwichkomplexe des Iridiums mit Tetramethylcyclopentadienyl als Ringligand

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Comparative mass spectrometric investigation of transition metal polymethylcyclopentadienylcarbonyl complexes

Cited by 9 publications

References 9 publications

Activation of Metal–Organic Precursors by Electron Bombardment in the Gas Phase for Enhanced Deposition of Solid Films

Activation of Metal–Organic Precursors by Electron Bombardment in the Gas Phase for Enhanced Deposition of Solid Films

Photochemical Reactions of the Rhenium Dinitrogen Phosphine and Phosphite Complexes Cp*Re(CO)(L)(N2) (L = P(OMe)3, P(OEt)3, P(OPh)3, P(OCH2)3CCH3, PPh3) in Hydrocarbon Solvents

Halbsandwichkomplexe des Iridiums mit Tetramethylcyclopentadienyl als Ringligand

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Photochemical Reactions of the Rhenium Dinitrogen Phosphine and Phosphite Complexes Cp*Re(CO)(L)(N₂) (L = P(OMe)₃, P(OEt)₃, P(OPh)₃, P(OCH₂)₃CCH₃, PPh₃) in Hydrocarbon Solvents