Single-crystal x-ray analysis of compounds with a covalent metal-metal bond. 5. Characterization of halogeno-bridged structures of three dimers of halogenobis(pentacarbonylmanganio)indium(III), [(Mn(CO)5)2In(.mu.-X)]2 (X = chlorine, bromine, iodine)

Abstract

The oxidative insertion of In'X into the Mn-Mn bond of Mn2(CO)io in the presence of xylene led to clusters of the type [(Mn(CO)s)2ln(M-X)]2 (X = Cl, Br, I). All three clusters were characterized by osmometric, thermogravimetric, mass spectroscopic, ir, and Raman spectroscopic measurements. X-ray structural analysis shows that the three clusters are isomorphous and have similar molecular structures. The central molecular fragment of each cluster contains a planar centrosymmetric four-membered In2X2 ring. Each In atom is bonded to two µatoms and to two Mn atoms in a distorted tetrahedral arrangement. The plane defined by the four Mn atoms is perpendicular to that defined by the 1^X2 atoms. The Mn-In-Mn angles of the three clusters have the following values: X = Cl, 123.59 (3)0; X = Br, 124.97 (3)°; X = I, 126.37 (4)°. The shortest intramolecular nonbonding O-O contact lengths correspond to equatorial CO ligands of the two pairs of Mn(CO)s ligands above or below the In2X2 plane (X = Cl, 2.877 (8) Á; X = Br, 2.896 (8) Á; X = I, 2.963 (9) A) and signify a dependence of the 0-0 repulsion interaction on the atomic size of the µatoms. A consequence of the repulsive effect connected with the nonbonded interaction of the equatorial CO groups of the different Mn atoms is their staggered arrangement. The In2X2 rings have obtuse -(µ-)-(X = Cl, 100.02 (5)°; X = Br, 97.42 (2)°; X = I, 94.35 (2)°) and acute (µ-)--(µ-) angles (X = Cl, 79.98 (5)°; X = Br, 82.58 (2)°; X = I, 85.65 (2)°) and the order of the nonbonded lengths In-In and X-X is In-In > X-X. These structural features of the 1^X2 rings are reversed with respect to corresponding features of the In2U ring of the compound [ 2 (µ-)]2 (acute -(µ-)angle, obtuse (µ-)--(µ-) angle, and the order of the length In-In < X-X), in which no comparable repulsion exists between the terminal ligands. The average In-X distances in the clusters examined are for X = Cl, 2.618 (2) Á, for X = Br, 2.757

Synthetic and structural studies on Group 13 complexes containing the M(CO)3(η-C5H5) fragment (M = Cr or Mo). Part 2. Complexes [InClx{M(CO)3(η-C5H5)}2]n–(x= 1, n= o; x= 2, n= 1)

“…' Mn(C0),,I3 and Cr(CO),(q-C,H,)14 and for these five complexes the M-Sn-M angles are 129.3( l), 128.3( 1 ), 128.6(3). 126.2( 1) and 130.2( 1)" and the Cl-Sn-Cl angles are 101.3( l), 98.1 ( l ) , 94.1 (6), 95.8( I ) and 95.0( 1)" respectively, i.c. a similar range of angles.…”

[Bis-μ-iodo-bis(tricarbonylrhenio)-(Re–Re)][μ-iodo-bis(tetracarbonylrhenio)-(Re–Re)]indium(III) and bis(pentacarbonylrhenio)(tetracarbonyl-bis-μ-iodo-rhenio)indium(III)

“…It is the first structurally determined sample with a spiro /Za third main-group metal attached to four transition-metal atoms. The structural analysis of the other title substance continues an earlier characterization of halogeno bridging bonds in similar compounds of the type {In[M'(CO)512}2(//,-X)2 (M' --Mn, Re) (Haupt, Wolfes & Preut, 1976. © 1989 International Union of Crystallography Experimental.…”

Application of Density Functional Theory in Coordination Chemistry: A Case Study of Group 13 Monohalide as a Ligand

“…Although a variety of systems including these lengths EX bridging between two metal centres have previously been characterised, complexes containing the heavier EX as terminal ligands have just previously been reported experimentally [85][86][87]. Dimeric complexes of the kind [(L n M) 2 E(μ-X) 2 E(ML n ) 2 ] or polymeric structure with sterically less hindered transition metal fragments [84,[121][122][123][124][125] are examples. The Lewis base coordinated at the group 13 centre can be used to segregate mononuclear systems in such circumstances [121,[126][127][128].…”

“…Dimeric complexes of the kind [(L n M) 2 E(μ-X) 2 E(ML n ) 2 ] or polymeric structure with sterically less hindered transition metal fragments [84,[121][122][123][124][125] are examples. The Lewis base coordinated at the group 13 centre can be used to segregate mononuclear systems in such circumstances [121,[126][127][128]. investigated the bonding nature of group 8 and 10 metal complexes with dihalogallyl ligands.…”