Oxidative Addition of Disulfides, Alkyl Sulfides, and Diphosphides to an Aluminum(I) Center

The aluminum­(I) compound NacNacAl (1) reacts with diphenyl disulfide and diethyl sulfide to form the respective four-coordinate bis­(phenyl sulfide) complex NacNacAl­(SPh)2 (2) and alkyl thiolate aluminum complex NacNacAlEt­(SEt) (3). As well, reaction of 1 with tetraphenyl diphosphine furnishes the bis­(diphenyl phosphido) complex NacNacAl­(PPh2)2 (4). Production of 3 and 4 are the first examples of C­(sp3)–S and R2P–PR2 activation by a main-group element complex. All three complexes were characterized by multinuclear NMR spectroscopy and X-ray crystal structure analysis. Furthermore, a variable-temperature NMR spectroscopic study was undertaken on 4 to study its dynamic behavior in solution.