A series of new chiral (iminophosphoranyl)ferrocenes, {
5-C
5H
4-(PPh
2=N-2,6-R
2-C
6H
3)}Fe{
5-C
5H
3-1-PPh
2-2-CH(Me)(Y)} (
1a, Y = NMe
2, R = Me;
1b, Y = NMe
2, R =
iPr;
1c, Y =OMe, R =
iPr), {
5-C
5H
4-(PPh
2=N-2,6-R
2-C
6H
3)}Fe{
5-C
5H
3-1-(PPh
2=N-2,6-R
2-C
6H
3)-2-CH(Me)(Y)} (
2a, R = Me, Y = NMe
2;
2b, R =
iPr, Y = NMe
2,;
2c, R = Me, Y = OMe),
and(
5-C
5H
5)Fe{
5-C
5H
4-1-PR
2-2-CH(Me)N=PPh
3} (
3a, R = Ph;
3b, R = C
6H
11), have beenprepared from the reaction of 1,1'-bis(diphenylphosphino)-2-[(dimethylamino)ethyl]ferrocenewith aryl azides (
1 and 2)
and the reaction of phosphine dichlorides (R
3PCl
2) with 1,1'-bis(diphenylphosphino)-2-(aminoethyl)ferrocene (
3), respectively. They form rhodium complexesof the type [Rh(NBD)(L)]ClO
4 (
4-
6; L =
1-
3), where the lig
and (L) adopts an
2(N,N) (
2) or
2(P,N) mode (
3), as expected. In the case of
1, a potential tridentate species, however, achelating bidentate mode through the -CH(Me)NMe
2 and -PPh
2 groups is realized withthe exclusion of the -P=NAr group from the coordination sphere, as confirmed by the X-raycrystal structure of [Rh(NBD)(
1b)]ClO
4 (
4b). The new lig
ands (
1-
3) exhibit exceptionallyhigh enantioselectivity (up to 99%)
and catalytic activity in the Rh-catalyzed asymmetrichydrogenation of (
E)-2-methylcinnamic acid, (
Z)-2-acetamidocinnamate,
and (
Z)-2-acetamidoacrylate.