Amidinato

This metathetical route was recently extended to the synthesis of amidinato complexes of Al, Ga, and In containing very bulky amidinate ligands with 2,6-Pr CgHs, adamantyl, m-terphenyl or 9-tiiptycenyl substituents at the central carbon atom. ... 

The metathetical route has also been employed to prepare bis(amidinato) aluminum chloride derivatives. The compounds [RC(NR )2]2A1C1 (R — Me, Bu R = Pr, Cy) were made that way from AICI3 and 2 equivalents of the corresponding lithium amidinate. ... 

The synthesis and characterization of the monomeric amidinato-indium(I) and thallium(I) complexes [Bu C(NAr)2]M[But(NAr(NHAr)] (M = In, Tl Ar = 2,6-Pr2CgH3) have been reported. Both compounds were isolated as pale yellow crystals in 72-74% yield. These complexes, in which the metal center is chelated by the amidinate ligand in an N, j -arene-fashion (Scheme 33), can be considered as isomers of four-membered Group 13 metal(I) carbene analogs. Theoretical studies have compared the relative energies of both isomeric forms of a model compound, In[HC(NPh)2]. ... 

Recently the first examples of complexes between the four-membered amidinato-Group 13 metal(l) heterocycles and transition metal fragments were reported. Complexes of the type CpFe(CO)2[M(X) But(NR)2 ] (M = Al, Ga, In X = Cl, Br R = Pri, Gy) were formed in salt-elimination reactions between Na[CpFe(CO)2] and [But(NR)2]MX2. A series of complexes between the four-membered amidinato-Group 13 metal(l) heterocycles and Group 10 metal(O) fragments have been prepared according to Scheme 35. ... 

Scheme 37 shows a reaction sequence leading to a mono(amidinato) indium bia(arylimido) complex. Subsequent treatment of the latter with Ti(NMe2)4 resulted in formation of the heterobimetallic In/Ti complex [But(NPr )2]In /t-NCgH3Pri-2,6 2Ti(NMe2)2 (cf. Sections 111.B.2 and V.A.l)." ... 

A bis(chelate) structure was found for the closely related germylene [MeC(NPr )2]2Ge, which was also made from GeCl2(dioxane) and 2 equivalents of the lithium amidinate (colorless crystals, 81%). The same synthetic approach was used to make bis(amidinato) metal dichlorides of silicon and germanium in high yields (83-95%). Rapid oxidative addition of chalcogen atom sources (styrene sulfide and elemental Se) to the germylene derivatives resulted in a series... 

Different coordination modes of the amidinate ligands were observed when the mixed-ligand amidinato-amido complexes of Ge(II) and Sn(II) were treated... 

Little progress has been made in the field of Group 15 metal amidinate and guanidinate derivatives. Only very recently some exciting results have been reported which demonstrate that this area may hold some real surprises and merits further exploration. It was found that amidinato ligands are capable to stabilize novel amidodiarsenes. Reduction of the four-membered ring As(III)... 

In a systematic study, it was demonstrated that, using a specially designed bulky benzamidinate ligand, it is possible to isolate mono(amidinato) dialkyl complexes over the full size range of the Group 3 and lanthanide metals, i.e., from scandium to lanthanum. The synthetic methods leading to the neutral and cationic bis(alkyls) are summarized in Scheme 56. Figure 18 displays the molecular structures of the cations obtained with Sc, Gd, and La. ... 

Several mono(amidinato) complexes of titanium containing the N,N -bis(trimethylsilyl)benzamidinato ligand have been prepared either by metathe-tical routes or ligand substitution reactions as outlined in Schemes 80 and 81. Trialkoxides are accessible as well as the dimeric trichloride, which can be... 

Titanium imido complexes supported by amidinate ligands form an interesting and well-investigated class of early transition metal amidinato complexes. Metathetical reactions between the readily accessible titanium imide precursors Ti( = NR)Cl2(py)3 with lithium amidinates according to Scheme 84 afforded either terminal or bridging imido complexes depending on the steiic bulk of the amidinate anion. In solution, the mononuclear bis(pyridine) adducts exist in temperature-dependent, dynamic equilibrium with their mono(pyiidine) homologs and free pyridine. 

Treatment of bis(pyridine) complexes of molybdenum and tungsten, M(f/ -allyl)Cl(CO)2(py)2 (M = Mo, W) with equimolar amounts of lithium amidinates Li[RC(NPh)2] (R = H, Me) afforded amidinato complexes of the type M(r -allyl)[RC(NPh)2](CO)2(py) (M = Mo, W). Reactions of the latter with acetonitrile, PEts, and P(OMe)3 have been investigated Free amidines react with M(r -allyl)Cl(CO)2(NCMe)2 according to Scheme 124 to give the corresponding bis(amidine) complexes. ... 

Treatment of the bis(amidine) derivatives with a strong base such as Bu Li leads to conversion to the corresponding amidinato(amidine) complexes which on further reaction with triethylphosphine loose the coordinated free amidine as illustrated in Scheme 125. ... 

The amidinato(pyridine) complexes also react with the triethylborane adduct of the NHC l,3-diisopropylimidazol-2-ylidene in toluene at reflux temperature to give the corresponding carbene complexes (Scheme 128). ... 

The resulting complexes comprise a novel amidinato-carbene ligand as well as a Ru-Si bond. ... 

Recently a novel chiral ferrocene-based amidinato ligand and its rhodium complexes have been described. The chiral N,N -bis(ferrocenyl)-substituted formamidine (N,N -bis[(S)-2- (lR)-l-(diphenylphosphino)ethyl ferrocen-l-yl]for-mamidine was prepared from commercially available (IR)-l-(dimethylamino) ethyl ferrocene by a multistep procedure in an overall yield of 29%. Deprotonation of the ligand with -butyllithium followed by addition of [RhCl2(COD)2] as illustrated in Scheme 167 yielded the corresponding (formamidinato)rhodium(l)... 

A promising recent extension of the aminopyridinato ligand concept involves the use of potentially tridentate amidinato-cyclopentadienyl ligands. Typical complexes with M = Ti, Zr are depicted in Scheme 171. Other heterocycles can be incorporated in the ligand system instead of the pyridine ring. ... 

Tridentate amido-amidinate ligands have also been constructed starting from (lR,2R)-diaminocyclohexane (cf. Section IV.D). Scheme 181 illustrates the use of such ligand in the preparation of novel amidinato-titanium alkoxide com-plexes. ... 

The guanidinate-supported titanium imido complex [Me2NC(NPr02l2Ti = NAr (Ar = 2,6-Me2C6H3) (cf. Section IILB.2) was reported to be an effective catalyst for the hydroamination of alkynes. The catalytic activity of bulky amidinato bis(alkyl) complexes of scandium and yttrium (cf. Section III.B.l) in the intramolecular hydroamination/cyclization of 2,2-dimethyl-4-pentenylamine has been investigated and compared to the activity of the corresponding cationic mono(alkyl) derivatives. 

Amidinate complexes of copper(I) and copper(II) have been found to catalyze the polymerization of carbodiimides. The copper catalysts are highly active even under air and oxygen. It was shown that the catalytic activity of an air-stable copper(II) amidinato complex is almost equal to that of reported air-sensitive titanium(IV) amidinate initiators. Scheme 225 illustrates the proposed reaction mechanism. ... 

Several patents dealing with the use of volatile metal amidinate complexes in MOCVD or ALD processes have appeared in the literature.The use of volatile amidinato complexes of Al, Ga, and In in the chemical vapor deposition of the respective nitrides has been reported. For example, [PhC(NPh)2]2GaMe was prepared in 68% yield from GaMes and N,N -diphenylbenzamidine in toluene. Various samples of this and related complexes could be heated to 600 °C in N2 to give GaN. A series of homoleptic metal amidinates of the general type [MIRCfNROilnl (R = Me, Bu R = Pr, BuO has been prepared for the transition metals Ti, V, Mn, Fe, Co, Ni, Cu, Ag, and La. The types of products are summarized in Scheme 226. The new compounds were found to have properties well-suited for use as precursors for atomic layer deposition (ALD) of thin films. 

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