24329-46-2

Upstream product

• 21961-74-0 1,1-dimethyl-1-germacyclobutane 
• 106-99-0 buta-1,3-diene 
• 120926-68-3 bis(dimethylgermyl)methane-iron tetracarbonyl 
• 75-87-6 chloral 
• 100-52-7 benzaldehyde 
• 176105-15-0 cis-bis-[(trimethylgermyl)methyl]-bis-(triphenylphosphine)platinum(II) 
• 176105-16-1 cis-bis-[(trimethylgermyl)methyl]-bis-(diphenylmethylphosphine)platinum(II) 

Relevant academic research and scientific papers

Syntheses, spectroscopic characteristics and thermolytic rearrangements of bis-[(trimethylgermyl) methyl]platinum(II) and bis-[(trimethylstannyl) methyl]platinum(II) complexes

The preparations and spectroscopic characteristics are reported of a series of (trimethylgermyl)methyl- and (trimethylstannyl)methyl- platinum(II) complexes with diene and P-donor ancillary ligands, cis-Pt(CH2GeMe3)2L2 (L = PPh3 or PPh2Me; L2 = dppe or cod) and cis-Pt(CH2SnMe3)2L2 (L = PPh3; L2 = cod). Thermolysis of toluene solutions of cis-Pt(CH2GeMe3)2(PPh3)2 leads to cis-Pt(Me)(CH2GeMe2CH2GeMe3)(PPh3)2 via β-alkyl migration, after (non-rate-limiting) phosphine dissociation. Estimated activation parameters (ΔH298 K? = 126 ± 3 kJ mol-1, ΔS? = + 17 ± 7 J mol-1 K-1 and hence ΔG298 K? = 121 ± 5 kJ mol-1) suggest that this system is more migration labile than its silicon analogue, primarily as a result of a lower activation enthalpy. While cis-Pt(CH2GeMe3)2(PPh2Me)2 reacts similarly but less readily, Pt(CH2GeMe3)2(dppe)2 is inert at operable temperatures. Thermolysis of Pt(CH2GeMe3)2(cod) generates 1,1,3,3,-tetramethyldi-1,3-germacyclobutane as the major organogermanium product, while from cis-Pt(CH2SnMe3)2(PPh3)2, 1,1,3,3-tetramethyldi-1,3-stannacyclobutane predominates. Mechanistic implications are discussed.

Kinetics and mechanism of the thermal decomposition of 1,1-dimethylgermetane

The gas-phase unimolecular decomposition of 1,1-dimethylgermetane has been investigated over the temperature range 683.9-751.2 K at pressures of ca. 15 Torr. Four products, cyclopropane, propene, ethene, and 1,1,2,2-tetramethylgermacyclopentane, are formed. Arrhenius parameters for the primary decomposition channels to (1) 1,1-dimethylgermene and ethene and (2) dimethylgermylene, cyclopropane, and propene are reported: (1) log k1/s-1 = 14.7 ± 0.4 - 63.1 ± 1.2 kcal mol-1/RT ln 10; (2) log k2/s-1 = 14.1 ± 0.3 - 60.7 ± 0.8 kcal mol-1/RT ln 10. (Matrix Presented) The surprisingly high activation energy for the 2 + 2 cycloreversion is interpreted in terms of a strong Ge-C bond dissociation enthalpy and/or reduced ring strain in the germetane.

Reactivity of [bis(dimethylgermyl)alkane]iron tetracarbonyls with carbonyl compounds

[Bis(dimethylgermyl)alkane]iron tetracarbonyls, Me2Ge(CH2)nGeMe2Fe(CO)4 (n = 1, 2), react with chloral, propionaldehyde, and benzaldehyde to give heterocyclic expansion reactions. Thermal decompositio