The Role of Secondary Interactions in Group 11 Metal Complexes Containing the Ferrocene Ligand FcCH₂NHpyMe in Supramolecular Structures

Abstract

The ferrocene ligand 6‐[(ferrocenylmethyl)amino]‐2‐picoline, FcCH2NHpyMe [Fc = (η5‐C5H5)Fe(η5‐C5H4)], has been prepared by treatment of FcCH2NMe2 with 6‐amino‐2‐picoline, NH2pyMe. The coordination chemistry with group 11 metals has been studied and several complexes with coordination of the metal atom to the pyridine nitrogen atom, such as [M(PPh3)(FcCH2NHpyMe)]OTf, [Au(C6F5)(FcCH2NHpyMe)] and [AuR3(FcCH2NHpyMe)] (M = Au, Ag; R3 = (C6F5)3, (C6F5)2Cl; OTf = trifluoromethanesulfonate), have been obtained. The complex [Cu(FcCH2NHpyMe)2]PF6 has also been synthesised with a probable coordination of the copper centre to the pyridine and amine nitrogen atoms. Deprotonation of the NH group allows the synthesis of dinuclear complexes of the type [M2(PPh3)2(FcCH2NpyMe)]X or [Au2(C6F5)(PPh3)(FcCH2NpyMe)] with a mixed pyridine−amide ligand. Some of the complexes have been characterised by X‐ray diffraction and show the presence of intramolecular aurophilic interactions in the dinuclear complex and intermolecular interactions leading to chains in the mononuclear complex. Other types of secondary bonds are present in these structures, such as hydrogen bonding and weak η2 interactions between the gold centre and the cyclopentadienyl ring. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Perfluoroarylgold complexes

“…19a), as was shown by DTF calculations [161], and intermolecular aurophilic contacts (see Table 1) that led to association into pairs in [Au(C 6 F 5 )(Fcpy)] [151] (Fig. 19b) and [Au(C 6 F 5 )(FcCH 2 pz)] [152] or into chains in the case of [Au(C 6 F 5 )(FcCH 2 NHpyMe)] [153] (Fig. 19c).…”

“…The gold(III) products that have been structurally characterized do not display intermolecular secondary interactions, aurophilic contacts or hydrogen bonds, and appear as monomers in the lattice with the exception of the 6-[(ferrrocenylmethyl)amino]-2-picoline derivatives [Au(C 6 F 5 ) 2 X(FcCH 2 NHpyMe)] (X = Cl, C 6 F 5 ) [153]. In these two species, apart from intramolecular N-H· · ·Au and N-H· · ·X hydrogen bonds, intermolecular C-H· · ·F and C-H· · ·Cl con- tacts create a 3D structure in the former or lead to the disposition of the molecules into planes in the latter.…”

“…For the isolation of perfluorophenylgold derivatives ligands with different donor atoms, such as sulfur [Fc(S 2 CNEt 2 ) 2 , Fc(SPh) 2 Tables 1 and 2 [151][152][153][154][155][156][157][158][159][160][161][162][163].…”

Gold(I) Complexes of N‐Heterocyclic Carbenes and Pyridines

“…The presence of a similar weak η 2 interaction has been observed. [29] [Au(Et 2 -bimy)(4-pic)][PF 6 ] (4) in Figure 5 has a C-Au-N angle of 179.31(15)°. The Et 2 -bimy and 4-pic rings are essentially coplanar.…”

Gold–Gold Interactions

“…Other bidentate ligands afford monomeric structures (Figure 2.44) such as 6-ferrocenylmethyl)amino-2-picoline (Figure 2.44a) [237], 8-aminoquinoline (2.33.c) [154], N-ferrocenecarbaldehide-2-mercaptoethylamino (Figure 2.44b) [238] 3-R-2-sulfanylpropeonate (Figure 2.44c) [239]. The bis-ortho-carborane compound shown in Figure 2.44d contains an intramolecular aurophilic interaction (3.119(2) Å).…”