title: 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 Na2S2O4 followed by reaction with excess PH2Ph, PH2Ad, or PHPh2 afforded [Fe(II)(F20-TPP)(PH2Ph)2] (1a), [Fe(II)(F20-TPP)(PH2Ad)2] (1b), [Fe(II)(F20-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)(PH2Ad)2] (3b) and [Ru(II)(Pc)(PH2Bu(t))2] (3c) were isolated by treating a mixture of [Ru(II)(Pc)(DMSO)2] and O=PCl2Ad or PCl2Bu(t) with LiAlH4. Hydrophosphination of CH2=CHR (R = CO2Et, CN) with [Ru(II)(F20-TPP)(PH2Ph)2] or [Ru(II)(F20-TPP)(PHPh2)2] in the presence of (t)BuOK led to the isolation of [Ru(II)(F20-TPP)(P(CH2CH2R)2Ph)2] (R = CO2Et, 5a; CN, 5b) and [Ru(II)(F20-TPP)(P(CH2CH2R)Ph2)2] (R = CO2Et, 6a; CN, 6b). Similar reaction of 3a with CH2=CHCN or MeI gave [Ru(II)(Pc)(P(CH2CH2CN)2Ph)2] (7) or [Ru(II)(Pc)(PMe2Ph)2] (8). The reactions of 4 with CH2=CHR (R = CO2Et, CN, C(O)Me, P(O)(OEt)2, S(O)2Ph), CH2=C(Me)CO2Me, CH(CO2Me)=CHCO2Me, MeI, BnCl, and RBr (R = (n)Bu, CH2=CHCH2, MeC[triple bond]CCH2, HC[triple bond]CCH2) in the presence of (t)BuOK afforded [Ru(II)(Pc)(P(CH2CH2R)Ph2)2] (R = CO2Et, 9a; CN, 9b; C(O)Me, 9c; P(O)(OEt)2, 9d; S(O)2Ph, 9e), [Ru(II)(Pc)(P(CH2CH(Me)CO2Me)Ph2)2] (9f), [Ru(II)(Pc)(P(CH(CO2Me)CH2CO2Me)Ph2)2] (9g), and [Ru(II)(Pc)(PRPh2)2] (R = Me, 10a; Bu(n), 10b; Bn, 10c; CH2CH=CH2, 10d; CH2C[triple bond]CMe, 10e; CH=C=CH2, 10f). X-ray crystal structure determinations revealed Fe-P distances of 2.2597(9) (1a) and 2.309(2) A (2bx 2 CH2Cl2) and Ru-P distances of 2.3707(13) (3b), 2.373(2) (3c), 2.3478(11) (4), and 2.3754(10) A (5b x 2 CH2Cl2). Both the crystal structures of 3b and 4 feature intermolecular C-H...pi interactions, which link the molecules into 3D and 2D networks, respectively.
authors.affiliation: Department of Chemistry and Open Laboratory of Chemical Biology of the Institute of Molecular Technology for Drug Discovery and Synthesis, The University of Hong Kong, Pokfulam Road, Hong Kong. jshuang@hkucc.hku.hk
authors.forename: Jie-Sheng
authors.initials: JS
authors.lastname: Huang
authors.forename: Guang-Ao
authors.initials: GA
authors.lastname: Yu
authors.forename: Jin
authors.initials: J
authors.lastname: Xie
authors.forename: Kwok-Ming
authors.initials: KM
authors.lastname: Wong
authors.forename: Nianyong
authors.initials: N
authors.lastname: Zhu
authors.forename: Chi-Ming
authors.initials: CM
authors.lastname: Che
mesh_terms: D000475:Alkenes / Q000737:chemistry; D018360:Crystallography, X-Ray; D006418:Heme / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D009942:Organometallic Compounds / Q000737:chemistry*; D010720:Phosphines / Q000138:chemical synthesis* / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet
chemical_list: D000475:Alkenes; D009942:Organometallic Compounds; D010720:Phosphines; C528283:ruthenium phthalocyanine; D010758:Phosphorus; D006418:Heme; D006859:Hydrogen; C044646:phosphine