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Synthese und spekroskopische charakterisierung von erdalkalimetallbis[bis(trimethylsilyl phosphaniden]—Molekülstrukturen von Ca[P(SiMe3)2]2· 2TMTA und Ba[P(SiMe3])2]2· 4THF

Journal of Organometallic Chemistry
Publication Date
DOI: 10.1016/0022-328x(93)83398-f


Abstract The metallation of bis(trimethylsilyl)phosphine by alkaline earth metal bis[bis(trimethylsilyl)amides] or magnesium dibutanide yields the corresponding alkaline earth metal bis[bis(trimethylsilyl phosphides]. With increasing size of the alkaline earth metal atom, an increasing low field shift of the 31P{ 1H} NMR resonance and an increasing value of the 1 J( 31P- 29Si) coupling constant is observable. Calcium-bis[bis(trimethylsilyl)phosphide] · 2TMTA · THF crystallizes in the monoclinic space group C2/ c with a = 1442.4(5), b = 1547.8(5), c = 2136.1(5) pm, β = 108.97(1) ° and Z = 4. The phosphorus atom is planar because of the steric demand of the three-dentate 1,3,5-trimethyl-1,3,5-triazinane ligands. The PSi distances have rather short values of 219 pm, whereas the CaP bond lengths of 299 pm exclude the possibility of backbonding from the phosphorus atom to the metal center. In barium-bis[bis(trimethylsilyl) phosphide] · 4THF, which crystallizes from THF in the monoclinic space group Cc ( a = 2905.9(11), b = 966.3(3), c = 1950.8(6)pm, β = 127.90(2) ° and Z = 4), the phosphorus atoms display a pyramidal coordination with angle sums of 345 ° The different BaP Si bond angles of about 104 ° and 137 ° in the trans-configurated molecule are remarkable.

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