Synthesis and Crystallographic Characterization of New Manganese(I) Complexes of Donor-Functionalized Indenes

Treatment of 1-P i Pr 2 -2-NMe 2 -indene ( 2 [H]) with BrMn(CO) 5 provided κ 2 - P, N -(2-NMe 2 -3-P i Pr 2 -indene)Mn(CO) 3 Br ( 4 ) in 73% yield. Addition of either AgBF 4 or AgSO 3 CF 3 to 4 yielded the corresponding inner-sphere tetrafluoroborate ( 5a ) and triflate ( 5b ) complexes in 62% and 65% yield, respectively. Deprotonation of 4, 5a, or 5b produced an intractable mixture of products. The cationic complex [κ 2 - P, N -(2-NMe 2 -3-P i Pr 2 -indene)Mn(CO) 4 ] + BF 4 - ( 6 ) was prepared in 30% yield by treating BrMn(CO) 5 with AgBF 4, followed by the addition of 2 [H]. The benzocymantrene η 5 -[ 2 ]Mn(CO) 3 was prepared in 56% yield via reduction of η 5 -(2-NMe 2 -3-P(S) i Pr 2 -indenyl)Mn(CO) 3 with Cl 3 SiSiCl 3 . Compound 2 [Li] reacts with BrMn(CO) 5 to give a complex product mixture, from which 4 and [κ 2 - P, N -(2-NMe 2 -3-P i Pr 2 -indene)Mn(CO) 4 ] + [Mn 2 (CO) 8 (μ-P i Pr 2 )] - ( 7 ) were isolated. 2-Dimethylaminoindene ( 1 [H]) was silylated to give 1-SiMe 3 -2-NMe 2 -indene ( 8 [H]) in 93% yield. Treatment of 8 [Li] with ClP i Pr 2, followed by the addition of BrMn(CO) 5, afforded κ 2 - P, N -(1-SiMe 3 -2-NMe 2 -3-P i Pr 2 -indene)Mn(CO) 3 Br ( 10 ) in 27% yield. Alternatively, addition of 8 [Li] to BrMn(CO) 5 followed by the addition of ClP i Pr 2 generated a mixture of products, from which the substituted 1,1‘-biindene rac -(2-NMe 2 -3-SiMe 3 -C 9 H 5 ) 2 ( rac - 12 ) was isolated. Treatment of 1 [Li] with BrMn(CO) 5 provided η 5 -(2-NMe 2 -indenyl)Mn(CO) 3 ( 11 ) in 41% yield. Single-crystal X-ray diffraction data for 4 ·0.5C 7 H 8, 5a ·0.5C 7 H 8, 5b, 6, η 5 -[ 2 ]Mn(CO) 3, 7 ·0.5C 7 H 8, 10, 11, and rac - 12 are reported.