Arene (toluene or benzene) solvated iron atoms, prepared by codeposition of iron atoms and excess arene, react with two equivalents H 2 SiCl 2 (or HSiMeCl 2 ) to yield (η 6 -arene)Fe(H) 2 (SiRCl 2 ) 2 (arene = toluene, benzene; R = H, Me). The hydride is acidic, and [(η 6 -toluene)Fe(H)(SiHCl 2 ) 2 ] - was produced, when (η 6 -toluene)Fe(H) 2 (SiHCl 2 ) 2 was treated with pyridine and 2,6-lutidine. The Si-H bond in [(η 6 -toluene)Fe(H)(SiHCl 2 ) 2 ] - is then activated with more pyridine and 2,6-lutidine. Polymerization has been observed, and [(η 6 -toluene)Fe(=SiCl 2 )(H)] - is proposed to be the intermediate. The structure of (η 6 -toluene)Fe(H) 2 (SiHCl 2 ) 2 was determined by X-ray single crystal diffraction: at -160°C, space group P2 1 /c, a = 7.651(1), b = 20.105(3), c = 9.252(2) 9, β = 110.88(4)°, Z = 4, V = 1330(1) 9 3 . In the NMR, three-bond-coupling between H-SiCl 2 and the hydride in (η 6 -toluene)Fe(H) 2 (SiHCl 2 ) 2 has been observed to be 5.2 Hz, one-bond-coupling between 2 9 Si and 1 H is 281 Hz, and two-bond-coupling between 2 9 Si and 1 H is 17.6 Hz. The two-bond-coupling between 2 9 Si and 1 H is 17.2 Hz in both (η 6 -toluene)Fe(H) 2 (SiMeCl 2 ) 2 and (η 6 -benzene)Fe(H) 2 (SiHCl 2 ) 2 . The one-bond-coupling between 1 3 C and 1 H of the coordinated benzene is 176 Hz.