Reduction of [Fe-III(Por)Cl] (Por = porphyrinato dianion) with Na2S2O4 followed by reaction with excess PH2Ph, PH(2)Ad, or PHPh2 afforded [Fe-II(F-20-TPP)(PH2Ph)(2)] (1a), [Fe-II(F-20-TPP)(PH(2)Ad)(2)] (1b), [Fe-II(F-20-TPP)(PHPh2)(2)] (2a), and [Fe-II(2,6-Cl2TPP)(PHPh2)(2)] (2b). Reaction of [Ru-II(Pc)(DMSO)(2)] (Pc = phthalocyaninato dianion) with PH2Ph or PHPh2 gave [Ru-II(Pc)(PH2Ph)(2)] (3a) and [Ru-II(Pc)(PHPh2)(2)] (4). [Ru-II(Pc)(PH(2)Ad)(2)] (3b) and [Ru-II(Pc)(PH2But)(2)] (3c) were isolated by treating a mixture of [Ru-II(Pc)(DMSO)(2)] and O=PCl(2)Ad or PCl2But with LiAlH4. Hydrophosphination of CH2=CHR (R = CO2Et, CN) with [Ru-II(F-20-TPP)(PH2Ph)(2)] or [Ru-II(F-20-TPP)(PHPh2)(2)] in the presence of (BuOK)-Bu-t led to the isolation of [Ru-II(F-20-TPP)(P(CH2CH2R)(2)Ph)(2)] (R = CO2Et, 5a; CN, 5b) and [Ru-II(F-20-TPP)(P(CH2CH2R)Ph-2)(2)] (R = CO2Et, 6a; CN, 6b). Similar reaction of 3a with CH2=CHCN or Mel gave [Ru-II(Pc)(P(CH2CH2CN)(2)Ph)(2)] (7) or [Ru-II(Pc)(PMe2Ph)(2)] (8). The reactions of 4 with CH2=CHR (R = CO2Et, CN, C(O)Me, P(O)(OD)(2), S(O)(2)Ph), CH2=C(Me)CO2Me, CH(CO2Me)=CHCO2Me, Mel, BnCl, and RBr (R = Bu-t, CH2=CHCH2, MeC CCH2, HC CCH2) in the presence of (BuOK)-Bu-t afforded [Ru-II(Pc)(PCH2CH2R)Ph-2)(2)] (R = CO2Et, 9a; CN, 9b; C(O)Me, 9c; P(O)(OD)(2), 9d; S(O)(2)Ph, 9e), [Ru-II(Pc)(P(CH2CH(Me)CO2Me)Ph-2)(2)] (9f), [Ru-II(Pc)(P(CH(CO2Me)CH2CO2Me)Ph-2)(2)] (9g), and [Ru-II(Pc)(PRPh2)(2)] (R = Me, 10a; Bu-n, 10b; Bn, 10c; CH2CH=CH2, 10d; CH2C=CMe, 10e; CH=C=CH2, 10f). X-ray crystal structure determinations revealed Fe-P distances of 2.2597(9) (1a) and 2.309(2) angstrom (2b center dot 2CH(2)Cl(2)) and Ru-P distances of 2.3707(13) (3b), 2.373(2) (3c), 2.3478(11) (4), and 2.3754(10) angstrom (5b center dot 2CH(2)Cl(2)). Both the crystal structures of 3b and 4 feature intermolecular C-H center dot center dot center dot pi interactions, which link the molecules into 3D and 2D networks, respectively.