Synthetic and single-crystal X-ray diffraction studies of CH2I2 and aryl iodide complexes of silver carboxylates and β-diketonates

Abstract

The silver() iodocarbon complexes5,5-hexafluoroaceylacetonate) and [Ag 4 (hfacac) 4 (1,2-I 2 C 6 H 4 ) 3 ] 11 have been prepared and structurally characterized by single-crystal X-ray diffraction. The silver carboxylate complexes all contain carboxylate-bridged Ag 2 (carboxylate-O,OЈ) 2 dimers (Ag᎐O 2.22-2.40 Å) with the intradimer Ag ؒ ؒ ؒ Ag distance varying in the range 2.9106(12) to 3.1527(14) Å which are the values observed for the alternating dimer units Ag 2 (O 2 CCF 3 ) 2 (H 2 O) 2 and Ag 2 (O 2 CCF 3 ) 2 observed in 5. In the complexes 1-3 the silver trifluoroacetate dimers are linked by I,IЈ-bridging I 2 R ligands with one 'short' Ag᎐I bond (2.94-3.05 Å) and one 'long' Ag᎐I bond (3.13-3.14 Å) per silver. In 4, 7 and 8 the Ag 2 (carboxylate-O,OЈ) 2 dimers are extended into a chain polymer via Ag 2 O 2 rings formed by co-ordination of each silver to an oxygen atom (Ag᎐O 2.33-2.51 Å) from an adjacent dimer. The 1,2-I 2 C 6 H 4 forms an I,IЈ bridge across the two silver atoms of the dimer unit in 7 [Ag᎐I 2.918(1) and 3.024(1) Å]. Complex 8 contains an acute angle bridging IC 6 H 5 [Ag᎐I 2.927(2) and 2.970(2) Å, Ag᎐I᎐Ag 61.4(1)Њ], whilst in 4 the IC 6 H 5 is semibridging [Ag᎐I 2.853(1) and 3.309(1) Å]. In complex 5 the two structurally different dimer units are bridged in a wide-angle fashion by p-IC 6 H 4 Me [Ag᎐I 2.9200(9) and 2.9333(8) Å, Ag᎐I᎐Ag 144.53(3)Њ]. Complex 6 contains eight-atom Ag 2) rings which are interlinked to give an alternating 8646 ring chain polymer with I,IЈbridging 1,2-I 2 C 6 H 4 across the two silvers of the six-atom rings [Ag᎐I 2.722(2) and 2.980(2) Å]. The hfacac complex 10 contains a tetranuclear unit in which the hfacac ligands both chelate and bridge whilst the p-iodotoluenes each bridge two silvers via η 1 -iodocarbon and η 2 -aryl co-ordination. Complex 11 is a tetranuclear unit in which three hfacac ligands both chelate and bridge whilst the fourth hfacac ligand bridges two silvers and forms a monodentate interaction with a third silver in a µ-O, η 1 -OЈ mode. One 1,2-I 2 C 6 H 4 ligand forms a monodentate interaction with a silver atom [Ag᎐I 3.064(3) Å] whilst the other two 1,2-I 2 C 6 H 4 molecules function as highly unsymmetrical bidentate ligands [Ag᎐I 2.691(2), 3.350(2) and 2.719(2) and 3.228(2) Å]. The Ag᎐I᎐C bond angles vary from 85.9(4)Њ in 11 to 108.70(12)Њ in 3.

Magnesium–halobenzene bonding: mapping the halogen sigma-hole with a Lewis-acidic complex

“…While metal⋯Cl–Ph complexes have been identified for Re, Zr and Rh, 9 a – d the cationic Al complex III represents a rare example for binding of a main group metal to a heavier halobenzene. 9 e Complexation of Ph–Br and Ph–I is limited to the softer metals Pd, Pt and Ag 10 and to the best of our knowledge, main group complexes with such ligands are unknown.…”

Designing neutral coordination networks with the aid of hydrogen bond mimicry using silver(i) carboxylates

“…3 CO 2 )(1,4-I 2 C 6 H 4 ), reported by Powell et al, wherein Ag 2 (CF 3 CO 2 ) 2 dimers (cf. XI) are linked via Ag-I bonded neutral ligands 25. …”

Structural variety of 5-fluoroarene-2-aminopyrimidine in comparison to 2-aminopyrimidine silver(i) coordination polymers: progress report and overview

“…They refer to a typical range for the distance between to metal centers of bridging TFA from 2.910 to 3.153 Å. 67 This leads to the conclusion that the TFA bridge in 4 is slightly stretched. Luminescence was regrettably not examined for this interesting system.…”