In
organometallic chemistry, A-frame complexes are
coordination compound
A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a surrounding array of bound molecules or ions, that are in turn known as ''ligands'' or complexing agents. Many ...
s that contain two
bridging bidentate
ligand
In coordination chemistry, a ligand is an ion or molecule ( functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's ele ...
s and a single atom bridge. They have the formula , where ''bd'' is a bidentate ligand like
dppm, and X and L are a wide variety of ligands. The term was coined to describe products arising from the oxidative addition to Rh(I)Rh(I) complexes.
Scope of compounds
A-frame complexes typically consist of a pair of square-planar metal centres. Consequently, this family of complexes is found for those metals that tend to adopt that geometry, Rh, Ir, Ni, Pd, Pt, and Au. In addition to dppm, the analogous tetramethyldiphosphine (dmpm) also forms such complexes as do some related ligands, such as
diphenyl-2-pyridylphosphine. The bridging site can be occupied by a variety of ligands, including CO,
SO,
NO, CH
2,
hydride
In chemistry, a hydride is formally the anion of hydrogen( H−). The term is applied loosely. At one extreme, all compounds containing covalently bound H atoms are called hydrides: water (H2O) is a hydride of oxygen, ammonia is a hydride of ...
, and chloride.
Preparation
A frame complexes are often produced by the addition of reagents of the type AX
2 to low valent complexes of dppm:
:2 M(0) + AX
2 + 2 dppm → M
2(μ-A)(dppm)
2X
2
Alternatively the group "A" can be added across a preformed M-M bond, as indicated by the
oxidative addition
Oxidative addition and reductive elimination are two important and related classes of reactions in organometallic chemistry. Oxidative addition is a process that increases both the oxidation state and coordination number of a metal centre. Oxid ...
of elemental sulfur:
[Tetsuro Murahashi, Hideo Kurosawa "Organopalladium complexes containing palladium/palladium bonds" Coordination Chemistry Reviews 2002, volume 231, pp. 207-228. {{doi, 10.1016/S0010-8545(02)00121-2]
:Pd
2(dppm)
2Cl
2 + S → Pd
2(μ-S)(dppm)
2Cl
2
References
Coordination complexes