Reactivity studies of silylene [PhC(NtBu)2](C5Me5)Si - reactions with [M(COD)Cl]2 (M = Rh(i), Ir(i)), S, Se, Te, and BH3Electronic supplementary information (ESI) available: NMR spectra and plots showing thermal ellipsoids of all structures. CCDC 1531726-1531730 and 1541874. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7dt00483d

The reactivity of recently introduced N-heterocyclic silylene [PhC(N t Bu) 2 ](C 5 Me 5 )Si was evaluated. Three different reaction pathways were studied: (1) coordination to a Lewis acid, (2) oxidation by chalcogenides, and (3) coordination to transition metal complexes. The reaction of the silylene with BH 3 led to the adduct [PhC(N t Bu) 2 ](C 5 Me 5 )Si(BH) 3 . Oxidation with the elemental chalcogens sulphur, selenium, and tellurium resulted in the corresponding silicon( iv )-chalcogenide compounds [PhC(N t Bu) 2 ](C 5 Me 5 )SiS, [PhC(N t Bu) 2 ](C 5 Me 5 )SiSe and [PhC(N t Bu) 2 ](C 5 Me 5 )SiTe. Treatment of the silylene with dimeric group 9 transition metal complexes [Ir(COD)Cl] 2 and [Rh(COD)Cl] 2 gave square planar coordinated transition metal silylene complexes [{PhC(N t Bu) 2 }(C 5 Me 5 )Si-Rh(COD)(Cl)] and [{PhC(N t Bu) 2 }(C 5 Me 5 )Si-Ir(COD)(Cl)]. The reactivity of N-heterocyclic silylene [PhC(N t Bu) 2 ](C 5 Me 5 )Si towards main group elements and transition metals was evaluated.