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Transition metal dinitrogen complex
Transition metal dinitrogen complexes are coordination compounds that contain transition metals as ion centers the dinitrogen molecules (N2) as ligands.
Transition metal complexes of N2 have been studied since 1965 when the first complex was reported by Allen and Senoff. This diamagnetic complex, [Ru(NH3)5(N2)]2+, was synthesized from hydrazine hydrate and ruthenium trichloride and consists of a [Ru(NH3)5]2+ centre attached to one end of N2. The existence of N2 as a ligand in this compound was identified by IR spectrum with a strong band around 2170–2100 cm−1. In 1966, the molecular structure of [Ru(NH3)5(N2)]Cl2 was determined by Bottomly and Nyburg by X-ray crystallography.
The dinitrogen complex trans-[IrCl(N2)(PPh3)2] is made by treating Vaska's complex with aromatic acyl azides. It has a planar geometry.
The first preparation of a metal-dinitrogen complex using dinitrogen was reported in 1967 by Yamamoto and coworkers. They obtained [Co(H)(N2)(PPh3)3] by reduction of Co(acac)3 with AlEt2OEt under an atmosphere of N2. Containing both hydrido and N2 ligands, the complex was of potential relevance to nitrogen fixation.
From the late 1960s, a variety of transition metal-dinitrogen complexes were made including those with iron, molybdenum and vanadium as metal centers. Interest in such complexes arises because N2 comprises the majority of the atmosphere and because many useful compounds contain nitrogen. Biological nitrogen fixation probably occurs via the binding of N2 to those metal centers in the enzyme nitrogenase, followed by a series of steps that involve electron transfer and protonation.
In terms of its bonding to transition metals, N2 is related to CO and acetylene as all three species have triple bonds. A variety of bonding modes have been characterized. Based on whether the N2 molecules are shared by two more metal centers, the complexes can be classified into mononuclear and bridging. Based on the geometric relationship between the N2 molecule and the metal center, the complexes can be classified into end-on or side-on modes. In the end-on bonding modes of transition metal-dinitrogen complexes, the N-N vector can be considered in line with the metal ion center, whereas in the side-on modes, the metal-ligand bond is known to be perpendicular to the N-N vector.
As a ligand, N2 usually binds to metals as an "end-on" ligand, as illustrated by [Ru(NH3)5N2]2+. Such complexes are usually analogous to related CO derivatives. This relationship is illustrated by the pair of complexes IrCl(CO)(PPh3)2 and IrCl(N2)(PPh3)2. In these mononuclear cases, N2 is both as a σ-donor and a π-acceptor. The M-N-N bond angles are close to 180°. N2 is a weaker pi-acceptor than CO, reflecting the nature of the π* orbitals on CO vs N2. For this reason, few examples exist of complexes containing both CO and N2 ligand.
Transition metal-dinitrogen complexes can contain more than one N2 as "end-on" ligands, such as mer-[Mo(N2)3(PPrn2Ph)3], which has octahedral geometry. In another example, the dinitrogen ligand in Mo(N2)2(Ph2PCH2CH2PPh2)2 can be reduced to produce ammonia. Because many nitrogenases contain Mo, there has been particular interest in Mo-N2 complexes.
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Transition metal dinitrogen complex
Transition metal dinitrogen complexes are coordination compounds that contain transition metals as ion centers the dinitrogen molecules (N2) as ligands.
Transition metal complexes of N2 have been studied since 1965 when the first complex was reported by Allen and Senoff. This diamagnetic complex, [Ru(NH3)5(N2)]2+, was synthesized from hydrazine hydrate and ruthenium trichloride and consists of a [Ru(NH3)5]2+ centre attached to one end of N2. The existence of N2 as a ligand in this compound was identified by IR spectrum with a strong band around 2170–2100 cm−1. In 1966, the molecular structure of [Ru(NH3)5(N2)]Cl2 was determined by Bottomly and Nyburg by X-ray crystallography.
The dinitrogen complex trans-[IrCl(N2)(PPh3)2] is made by treating Vaska's complex with aromatic acyl azides. It has a planar geometry.
The first preparation of a metal-dinitrogen complex using dinitrogen was reported in 1967 by Yamamoto and coworkers. They obtained [Co(H)(N2)(PPh3)3] by reduction of Co(acac)3 with AlEt2OEt under an atmosphere of N2. Containing both hydrido and N2 ligands, the complex was of potential relevance to nitrogen fixation.
From the late 1960s, a variety of transition metal-dinitrogen complexes were made including those with iron, molybdenum and vanadium as metal centers. Interest in such complexes arises because N2 comprises the majority of the atmosphere and because many useful compounds contain nitrogen. Biological nitrogen fixation probably occurs via the binding of N2 to those metal centers in the enzyme nitrogenase, followed by a series of steps that involve electron transfer and protonation.
In terms of its bonding to transition metals, N2 is related to CO and acetylene as all three species have triple bonds. A variety of bonding modes have been characterized. Based on whether the N2 molecules are shared by two more metal centers, the complexes can be classified into mononuclear and bridging. Based on the geometric relationship between the N2 molecule and the metal center, the complexes can be classified into end-on or side-on modes. In the end-on bonding modes of transition metal-dinitrogen complexes, the N-N vector can be considered in line with the metal ion center, whereas in the side-on modes, the metal-ligand bond is known to be perpendicular to the N-N vector.
As a ligand, N2 usually binds to metals as an "end-on" ligand, as illustrated by [Ru(NH3)5N2]2+. Such complexes are usually analogous to related CO derivatives. This relationship is illustrated by the pair of complexes IrCl(CO)(PPh3)2 and IrCl(N2)(PPh3)2. In these mononuclear cases, N2 is both as a σ-donor and a π-acceptor. The M-N-N bond angles are close to 180°. N2 is a weaker pi-acceptor than CO, reflecting the nature of the π* orbitals on CO vs N2. For this reason, few examples exist of complexes containing both CO and N2 ligand.
Transition metal-dinitrogen complexes can contain more than one N2 as "end-on" ligands, such as mer-[Mo(N2)3(PPrn2Ph)3], which has octahedral geometry. In another example, the dinitrogen ligand in Mo(N2)2(Ph2PCH2CH2PPh2)2 can be reduced to produce ammonia. Because many nitrogenases contain Mo, there has been particular interest in Mo-N2 complexes.