Kurt Geibel

Chemie polyfunktioneller moleküle: LXXVII. Das reaktionsverhalten von bis(diphenylphosphino)amin gegenüber di-μ-chloro-bis[dicarbonylrhodium(I)]☆

Abstract This paper describes the direct synthesis of the A-frame complex Rh 2 (μ-CO)(μ-Ph 2 PNHPPh 2 ) 2 Cl 2 ·CH 3 OH·O(C 2 H 5 ) 2 (IV′) from [Rh(μ-Cl)(CO) 2 ] 2 and Ph 2 -PNHPPh 2 (I). The intermediates formed, [Rh 2 (μ-CO)(μ-Cl)(μPh 2 PNHPPh 2 ) 2 (CO) 2 Cl·0.5O (C 2 H 5 ) 2 (Va), Rh 2 (μ-CO)(μ-Cl)(μPh 2 PNHPPh 2 ) 2 (CO)(Cl)·0.5O(C 2 H 5 ) 2 (VI), and the by-product [Rh(CO)(Cl)(Ph 2 PNHPPh 2 )·(1–2) CH 3 OH] n (VII), were isolated and characterized. Compound IV′ reacts with CO to yield Va, which undergoes a metathesis reaction with NaBPh 4 or NH 4 PF 6 , to give [Rh 2 (μ-CO)(μ-Cl)(μ-Ph 2 PNHPPh 2 ) 2 (CO) 2 ]BPh 4 ·CH 3 OH (Vb) and [Rh 2 (μ-CO)(μ-Cl)(μ-Ph 2 PNOPPh 2 ) 2 (CO) 2 ]PF 6 (Vc). The reaction of [Rh(μ-Cl)(CO) 2 ] 2 with I in a molar ratio of 3 4 , yields (Rh 2 (μ-CO)(μ-Cl)-(μ-Ph 2 PNHPPh 2 ) 2 (CO) 2 ][Rh(CO) 2 Cl 2 ]·2CH 3 OH (Vd). The reaction of [Rh(μ-Cl)(CO) 2 ] 2 with I in a closed tube (molar ratio 1 2 ) yields [Rh 2 (μ-CO)(μ-Cl) (μ-Ph 2 PNHPPh 2 ) 2 (CO) 2 ]Cl·CH 3 OH (Va′). The compound [Rh 2 (gm-Cl)-(μ-Ph 2 PNHPPh 2 ) 2 (CO) 2 ]BPh 4 ·CH 3 OH (VIII) is obtained from Vb in methanolic solution with CO elimination. From a solution of VIII in CH 2 Cl 2 , [Rh 2 (μ-Cl)(μ-CH 2 Cl 2 ) (μ-Ph 2 PNHPPh 2 ) 2 (CO) 2 ]BPh 4 -O(C 2 H 5 ) 2 (IX) precipitates on adding diethyl ether. Red IX in methanolic solution converts back to the yellow VIII. The structures of the new compounds are determined on the basis of 31 P{ 1 H} NMR, 1 H NMR, IR, ESR and MS spectroscopic and conductometric data.

Metallomethane : III. 1H- und 13C-NMR-untersuchungen an chloroquecksilbermethanen CH4−n(HgCl)n

Abstract 1 H and 13 C NMR data are presented for chloromercurimethanes CH 4− n (HgCl) n (1 ≦ n ≦ 4). The chemical shifts indicate increasing deshielding of 1 H, 13 C and 199 Hg nuclei with increasing n . The coupling constants 1 J (CH) and 2 J (HgH) in the series are discussed in terms of changing 2 s -contribution from carbon to the CH and CHg bonds. The 1 J (HgC) couplings cannot be interpreted consistently with the other couplings on the basis of Fermi contact interaction alone; possible explanations for these discrepancies are suggested. On the whole, increasing degree n of mercuration seems to cause increasing positive charges on hydrogen, carbon and mercury atoms and weakening of the CHg bonds.

Phosphazine : VIII. IR- und NMR-spektren von α-ketotriphenylphosphazinen☆

Abstract The results of IR- and NMR-spectroscopic investigations on α-ketotriphenylphosphazines are reported. The structure of these compounds is discussed.

Chemie polyfunktioneller Liganden, 64 [1]. Über Hydridoiridium(III)-Komplexe des N.N-Bis(diphenylphosphino)-p-tolylamiii Chemistry of Polyfunctional Ligands, 64 [1]. On Hydridoiridium(III) Complexes of N,N-Bis(diphenylphosphino)-p-tolylamine

H2 reacts with [Ir{(Ph2P)2N-p-C6H4CH3}2]Cl · 3 C6H6 (1) to give cis-[Ir(H)2{(Ph2P)2N-p-C6H4CH3}2]Cl · CH2Cl2 (2a). By reaction of 2a with NaBPh4 cis-[Ir(H)2{(Ph2P)2N-p-C6H4CH3}2]BPh4 (2 b) is obtained. Refluxing of 2a in CH2Cl2 yields trans-[lr(H)2{(Ph2P)2N-p-C6H4CH3}2]Cl · 1/2 CH2Cl2 (3a), which undegoes metatheses with NaBPh4 to trans-[Ir(H)2{(Ph2P)2N-p-C6H4CH3}2]BPh4 (3b). 3a is also formed by refluxing of 1 in methanol in the presence of oxygen. Oxidative addition of HCl to 1 and reaction with NaBPh4 yields trans-[Ir(H)(Cl){(Ph2P)2N-p-C6H4CH3}2]BPh4 (4b). The new compounds are characterised by their IR, Raman, 31P{1H} PFT and 1H NMR Spectra