Primary and secondary phosphine complexes of iron porphyrins and ruthenium phthalocyanine: Synthesis, structure, and P-H bond functionalization

Abstract

Reduction of [Fe III(Por)Cl] (Por = porphyrinato dianion) with Na 2S 2O 4 followed by reaction with excess PH 2Ph, PH 2Ad, or PHPh 2 afforded [Fe II(F 20-TPP)(PH 2Ph) 2] (1a), [Fe II(F 20-TPP)(PH 2Ad) 2] (1b), [Fe II(F 20-TPP)(PHPh 2) 2] (2a), and [Fe II(2,6-Cl 2TPP)(PHPh 2) 2] (2b). Reaction of [Ru II(Pc)(DMSO) 2] (Pc = phthatocyaninato dianion) with PH 2Ph or PHPh 2 gave [Ru II(Pc) (PH 2Ph) 2] (3a) and [Ru II(Pc)(PHPh 2) 2] (4). [Ru II(Pc)(PH 2Ad) 2] (3b) and [Ru II(Pc)(PH 2Bu t) 2] (3c) were isolated by treating a mixture of [Ru II(Pc)(DMSO) 2] and O=PCl 2Ad or PCl 2Bu t with LiAlH 4. Hydrophosphination of CH 2=CHR (R = CO 2Et, CN) with [Ru II(F 20-TPP)(PH 2Ph) 2] or [Ru II(F 20-TPP)(PHPh 2) 2] in the presence of tBuOK led to the isolation of [Ru II(F 20-TPP) (P(CH 2CH 2R) 2Ph) 2] (R = CO 2Et, 5a; CN, 5b) and [Ru II(F 20-TPP)(P(CH 2CH 2R)Ph 2) 2] (R = CO 2Et, 6a; CN, 6b). Similar reaction of 3a with CH 2=CHCN or Mel gave [Ru II(Pc)(P(CH 2CH 2CN) 2Ph) 2] (7) or [Ru II(Pc)(PMe 2Ph) 2] (8). The reactions of 4 with CH 2=CHR (R = CO 2Et, CN, C(O)Me, P(O)(OEt) 2, S(O) 2Ph), CH 2=C(Me)CO 2Me, CH(CO 2Me)=CHCO 2Me, Mel, BnCl, and RBr (R = nBu, CH 2=CHCH 2, MeC≡CCH 2, HC≡CCH 2) in the presence of tBuOK afforded [Ru II(Pc)(P(CH 2CH 2R)Ph 2) 2] (R = CO 2Et, 9a; CN, 9b; C(O)Me, 9c; P(O)(OEt) 2, 9d; S(O) 2Ph, 9e), [Ru II(Pc)(P(CH 2CH(Me)CO 2Me)Ph 2) 2] (9f), [RU II(PC) (P(CH(CO 2Me)CH 2CO 2Me)Ph 2) 2] (9g), and [Ru II(Pc)(PRPh 2) 2] (R = Me, 10a; Bu n, 10b; Bn, 10c; CH 2CH=CH 2, 10d; CH 2C≡CMe, 10e; CH=C=CH 2, 10f). X-ray crystal structure determinations revealed Fe-P distances of 2.2597(9) (1a) and 2.309(2) Å(2b·2CH 2Cl 2) and Ru-P distances of 2.3707(13) (3b), 2.373(2) (3c), 2.3478(11) (4), and 2.3754(10) Å(5b·2CH 2Cl 2). Both the crystal structures of 3b and 4 feature intermolecular C-H ⋯ π interactions, which link the molecules into 3D and 2D networks, respectively. © 2008 American Chemical Society.