Cyclometalated titanium and zirconium complexes stabilised by a new silylmethylene-linked tetradentate triamidophosphine.

The silylmethylene-linked triamidophosphine P(CH2SiMe2NHPh)3 was isolated in form of its tri-lithium salt Li3[P(CH2SiMe2NPh)3]·2.5Et2O (1·2.5Et2O) and employed for the synthesis of titanium and zirconium complexes. Starting from 1·2.5Et2O, the chlorido complexes [κ(4)-N,N,N,P-PN3]MCl (4-M, M = Ti, Zr) were prepared and examined with respect to alkylation. Upon reaction of 4-Ti with (trimethylsilyl)methyl lithium, intra-ligand cyclometalation at one of the ortho-N-phenyl positions was observed and the resulting thermally stable titanazetidine [κ(5)-N,N,N,P,C-N2P(NC)]Ti (5-Ti) isolated. Similarly, the related zirconazetidine [κ(5)-N,N,N,P,C-N2P(NC)]Zr(THF) (5-Zr) was isolated upon reaction of 4-Zr with Bn2Mg(THF)2. Using LiCH2PMe2 as alkyl transfer reagent, both complexes 4-M were converted to the corresponding phosphametallacyclopropanes [κ(4)-N,N,N,P-PN3]M(κ(2)-C,P-CH2PMe2) (7-M, M = Ti, Zr). Upon gentle heating, complexes 7-M were cleanly converted to the cyclometalated species 5-M and trimethylphosphine. These results are discussed in the context of related amidophosphine and triamidoamine complexes.

Rat adrenal medulla: levels of chromogranins, enkephalins, dopamine beta-hydroxylase and of the amine transporter are changed by nervous activity and hypophysectomy.

The levels of several constituents of chromaffin granules were determined in rat adrenal medulla after treatment with insulin or reserpine and after hypophysectomy. Insulin treatment induced increased levels of enkephalins, dopamine beta-hydroxylase, the amine carrier and of chromogranin B whereas catecholamines, cytochrome b-561 and chromagranin A remained slightly below control levels. Administration of reserpine led to similar changes with the exception of the enkephalins which increased much less. After hypophysectomy, chromogranin A was reduced to low levels; dopamine beta-hydroxylase, the amine carrier and catecholamines showed an intermediate reduction, whereas the other components remained at control levels. We can conclude that nervous stimulation of the adrenal medulla (by insulin and reserpine) induces the synthesis of enkephalins, dopamine beta-hydroxylase, the amine carrier and chromogranin B whereas the level of chromogranin A apparently depends on corticosteroids. Thus, major components of the secretory content and the membranes of chromaffin granules are regulated separately, which allows the biogenesis of chromaffin granules with a significantly altered composition.