Novel ‘bis(phosphine) pincer’ complexes of iridium based on ferrocene and ruthenocene

have been prepared. The reaction of ‘1,3-bis((di-tert-butylphosphino)methyl)metallocenes’ [ t-

Bu
P,CH,PM] (M = Fe, 10; M = Ru, 13) with [Ir(COE) 2Cl]2 in refluxing toluene leads to the
corresponding chloro hydrido pincer complexes as a mixture of Hydrogen-endo (M = Fe, 11; M
= Ru, 14) and H-exo-IrH(Cl)[ t-BuP,C,PM] (M = Fe, 12; M = Ru, 15) isomers. Treatment of
compounds 11, 12 and 14, 15 with sodium hydride in hot cyclooctane generates corresponding
dihydrido complexes IrH2[t-BuP,C,PM] (M = Fe, 6; M = Ru, 7). Reactivity of the chelated iridium
atom in hydrido iridium pincer complexes and oxidation centered at the iron atom of ferrocene
based pincer complexes were studied. Complexes Hydrogen- exo-IrH(Cl)(CO)[ t-BuP,C,PFe] (20),
Ir(CO)[t-BuP,C,PFe] (21) and Ir(CO)[2,6-(tBu2PO)2C6H3] (30) were characterized by Xray
crystallography. On the basis of νCO values for carbonyl iridium derivatives, electronic
characteristics of the corresponding fragments {Ir[ t-BuP,C,PM]}n (n = 0, +1) were elucidated.
Complexes 6 and 7 reveal unprecedented catalytic activity in cyclooctane dehydrogenation in the
presence of tert-butylethylene as a hydrogen acceptor:□ turnover numbers 3300, 2571, and 1843
were obtained for 6, 7, and the known complex IrH 2[2,6-(tBu2PO)2C6H3] (4c), respectively, at 180
°C for 8 h. The high catalytic activity for 6 and 7 and the difference in the catalytic activity of
these “isostructural” complexes are discussed in terms of steric and electronic effects [200].

Bu2Pt

Ir

PtBu2
Fe

A series of metal di-mnt complexes [mnt = 1,2-dithiolatomaleonitrile] with the

‘trimethylammonium methylferrocene’ cation have been prepared and characterized using Xray
diffraction, magnetic susceptibility and differential scanning calorimetry measurements. The
complexes have the formulaes (FcCH 2NMe3)[Ni(mnt)2] (2), (FcCH2NMe3)[Pt(mnt)2] (3), and
(FcCH2NMe3)2 [Cu(mnt)2] (4) (where Fc = ferrocene). At 300 K, the crystal structures of 1:1
complexes 2 and 3 are very similar. They consist of pairs of [M(mnt) 2]- in a slipped
configuration packed in stacks. Each [M(mnt) 2]- stack is separated from adjacent stacks by two
columns of cations. Within the pairs, the [M(mnt) 2]- anions interact via short M···S contacts,
while there are no short contacts between the pairs. Complex 4, which have a 2:1 stoichiometry,
exhibits a markedly different packing arrangement of the anionic units. Due to the special
position of the Copper atom in the asymmetric unit cell, [Cu(mnt) 2]2- dianions are completely
isolated from each other. The magnetic susceptibility behavior of the nickel complex is
consistent with the presence of magnetically isolated, antiferromagnetically (AF) coupled
[Ni(mnt)2]- pairs with the AF exchange parameter, J = −840 cm -1. The platinum complex
undergoes an endothermic structural phase transition (T p) at 247 K. Below Tp its structure is
characterized by the formation of magnetically isolated [Pt(mnt) 2]22- dimers in an eclipsed
configuration with short Pt···Pt and S···S contactsbetween monomers. In the magnetic properties,
the structural changes reveal themselves as an abrupt susceptibility drop implying a substantial
increase of the AF exchange parameter. A mechanism of the phase transition in the platinum
compound is proposed. For compound 4, paramagnetic behavior were observed[201].

Palladium P,C,P pincer complexes based on ferrocene were synthesized for the first time.
The reaction of the ‘1,3-bis((dialkylphosphino)methyl)ferrocenes’ {1,3- (R 2PCH2)2C5H3}Fe(C5H5)
(2a, R = Pri; 2b, R = But) with PdCl2(NCPh)2 in refluxing ‘2- methoxyethanol’ leads to the
corresponding pincer complexes PdCl[{2,5- (R 2PCH2)2C5H2}Fe(C5H5)] (3a,b). The ferrocene
based binuclear compound 3b reacts with [Cp2Fe]PF6 to form the ‘ferrocenium based
pincer’ complex {PdCl[{2,5- (Bu t PCH ) C H }Fe(C H )]}PF (4b), and this is the first
example
2 of
2 2ferrocene
5 2 based
5 5 phosphine
6 chelate oxidation centered on the iron atom. Treatment of
complexes 3a,b with NaBH4 in refluxing ethanol affords the complexes Pd(BH 4)[{2,5-
(R2PCH2)2C5H2}Fe(C5H5)] (5a, R = Pri; 5b, R = But), containing a BH4− group coordinated to the
metal in the rarely occurring unidentate mode. The structures of 3a,b and 5b were confirmed by
Xray analyses. Cyclic voltammetric investigations of complexes 2b and 3a, b were also reported.
The structural and spectroscopic features of the ‘palladium ferrocene based pincer’ complexes
were discussed and compared with those of related compounds [202].
PR2

H
R2P Cl R2P H
B
Pd Pd H
H
PR2 PR2
Fe Fe PR2
PdCl2(NCPh)2 NaBH2 Fe
EtOH/RT
MeOCH2CH2OH
 Covalent attachment of one and two NP moieties to a ferrocenyl unit provides
organometallic ligands ‘1,8-naphthyrid-2-yl-ferrocene (FcNP)’ and ‘1,1′-bis(1,8-naphthyrid-
2- yl)ferrocene (FcNP2)’. Co-ordination of FcNP to transition metal ions Iron(II), Copper(II),
Zinc(II) and Cadmium (II) provides [FeCl2(κN8-FcNP)2] (1), [Cu(κN8-FcNP)2(NO3)2] (2),
[Zn(κN8-FcNP)4][OTf]2 (3), and [Cd(κN8-FcNP)2(κ2N1,N8-FcNP)2][BF4]2 (4), respectively.
Dirhodium (II) compound [Rh2(µ-FcNP)2(µ-O2CCH3)2(H2O)][OTf]2 (5) is isolated when
acetonitrile solvated [Rh2(µ-O2CCH3)2]2+ is employed as a precursor. Diverse bonding
modes of the NP unit, including monodentate, bidentate chelating or binuclear bridging are
revealed in these FcNP clusters. ‘Metallamacrocycles’ [M 2(FcNP2)2][X]2 (M = Cu, X = ClO4
(6); M = Ag, X = OTf (7)), [PdCl2(FcNP2)] (8), and [ZnCl2(FcNP2)]4 (10) were obtained by
the reaction of CuClO4, AgOTf, Pd(C6H5CN)2Cl2 and ZnCl2 with FcNP2 in 1:1 ratios.
Treatment of Copper(II) and FcNP2 in a 2:1 ratio provides [Cu 2(FcNP2)][ClO4]2 (9).
Molecular structures of compounds 1−10 have been determined by Xray diffraction studies.
Interco version between 1:1 dimer 6 and 2:1 dimer 9 occurs by the addition of a requisite
amount of Copper(I) or FcNP 2. ESI-MS experiments reveal that the predominant species is
the 1:1 complex {Cu(FcNP2)}1+ in solution for both 6 and 9. Synthesis, structures, mass
spectroscopy, and electrochemistry of the transition metal compounds of FcNP and FcNP 2
are discussed [203].