Platinum(II) cis-dimethyl and cis-dineopentyl complexes bearing the alkyl-substituted bis-NHC ligands L t-Bu , L Me , and L i-Pr (L t-Bu = 1,1′-di-tert-butyl-3,3′-methylenediimidazolin-2,2′-diylidene, L Me = 1,1′-dimethyl-3,3′-methylenediimidazolin-2,2′-diylidene, L i-Pr = 1,1′-diisopropyl-3,3′methylenediimidazolin-2,2′-diylidene) as well as novel cisalkyl chloro and cis-alkyl hydrido compounds were synthesized. The reactivity of the dimethyl complexes toward dichloromethane and methanol was investigated. Reductive elimination of alkanes from cis-alkyl hydrido complexes requires much higher temperatures than in related bisphosphine systems, which limits their applicability for the generation of reactive, bent platinum(0) d 10 -ML 2 fragments for bond-activation chemistry. The platinum(II) complexes were characterized by NMR and IR spectroscopy, mass spectrometry, elemental analysis, and X-ray diffraction in most cases.