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Reaction of Fe2(CO)9 with Ph2P(CH2) n SnR2R‘ (n = 2, R‘ = Ph, SnR2 = SnPh2, SnPhMe, R‘ = Me, SnR2 = SnMe2; n = 1, 3, SnR2R‘ = SnPh3) results in the formation of (CO)5-x Fe[PPh2(CH2) n SnR2R‘] x (x = 1, 2). Upon UV irradiation, the chelated (phosphinoalkyl)stannyl complexes (CO)3(R‘)FePPh2(CH2) n SnR2 are obtained by intramolecular oxidative addition of the Sn−R‘ group. The complexes mer-(CO)3(H)(R‘3Si)FePPh2(CH2)3SnPh3 (SiR‘3 = SiMePh2, Si(OMe)3) are formed at −50 °C from (CO)4Fe(H)SiR‘3 and Ph2P(CH2)2SnPh3. While the SiMePh2 derivative is converted to the chelated complex (CO)3(Ph)FePPh2(CH2)2SnPh2 by HSiMePh2 elimination upon heating, the Si(OMe)3 derivative does not give the intramolecular oxidative addition. Photochemical reaction of (CO)3(Ph)FePPh2(CH2)2SnPh2 with Ph2P(CH2)2SnPh3 gives the substitution product (CO)2(Ph)Fe[PPh2(CH2)2SnPh2]PPh2(CH2)2SnPh3. While a second oxidative addition to the iron center by the dangling SnPh3 group is not possible, the Sn−Ph group readily adds to a (Ph3P)2Pt fragment to give (CO)2(Ph)Fe[PPh2(CH2)2SnPh2]PPh2(CH2)2SnPh2Pt(Ph)(PPh3)2. The related complex (CO)3(H)[(MeO)3Si]FePPh2(CH2)2SnPh2Pt(Ph)(PPh3)2 is similarly obtained from (CO)3(H)[(MeO)3Si]FePPh2(CH2)2SnPh3.

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