Metallaaromatics Containing Main‐group Heteroatoms

Abstract

Metallaaromatics are metallacycles that are derived from the formal replacement of a carbon atom in the framework of organic aromatics with a metal fragment. As an important subclass of metallaaromatics, metallaaromatics that contain main‐group heteroatoms have attracted considerable attention. In the past ten years, we have developed several new methods to construct metallaaromatics as well as those containing main‐group heteroatoms, such as metallapyridine, metallapyridinium, metallapyridyne, metallafuran, metallabenzothiazole, metallabenzoxazole, metallabenzthiophene, aza‐metallapentalene and some novel tricyclic/tetracyclic metallaaromatics. In addition, interesting reactions such as the first hetero‐Diels Alder reaction between 1‐metalla‐1,3‐dienes and nitriles, the first intramolecular nucleophilic aromatic substitution (SNAr) reaction of metallabenzene, and the first iodine‐mediated electrophilic cyclizations of a metallabenzene complex were demonstrated. In this account, recent and novel approaches for their synthesis and property analyses are summarized. The structural diversity and unique properties of metallaaromatics containing main‐group heteroatoms will strongly inspire further investigation of these species and provide a wide range of potential applications.

Synthesis and Characterization of Photothermal Osmium Carbolong Complexes

“…Further study showedt hat complex 4 was produced by protonation of complex 2 by HBF 4 generated in situ (see Figure S4 for the in situ NMR reactiono fc omplex 2 with HBF 4 ). This result was further (6),C 2 ÀC3 1.414 (5), C3ÀC4 1.375(5), C4ÀC5 1.409(5), C5ÀC6 1.368(6),C 6 ÀC7 1.410(6), C7ÀC8 1.444(6), C8ÀC9 1.347(6), C9ÀC10 1.485 (6), C10ÀC111.417(6), C11ÀC12 1.396 (6);O s1-C1-C2 118.9(3), C1-C2-C3 114.0(4), C2-C3-C4 113.8(3), C3-C4-Os1 118.8(3), C4-Os1-C1 74.5(1), Os1-C4-C5 117.6(3), C4-C5-C6 114.6(3), C5-C6-C71 14.3(3), C6-C7-Os1 118.7(3), C7-Os1-C4 74.8(2), C7-Os1-C1072.5(2), C7-Os1-C11 97.7(2),C 7-C8-C9 115.4(4), C8-C9-C10 114.1(4), C9-C10-C11122.4(4), C10-C11-Os1 70.1(2), C11-Os1-C12 36.0(1), C11-C12-Os1 70.1(3), C10-C11-C12 122.2(4), Os1-C11-C128 2.2(3), P1-Os1-P2 170.4 (4).…”

“…Crystal data for 4:[ C 78 H 63 OsP 3 ](BF 4 ) 2 ·CH 2 Cl 2 (M = 1541.94 gmol À1 ): triclinic, crystal dimensions 0.40 0.40 0.30 mm, space group P1 (no. 2), a = 13.0475 (3), b = 15.8684 (6), c = 19.3296(8) , a = 73.996 (4), b = 80.198(3), g = 83.024(3)8, V = 3779.0(2) 3 , Z = 2, T = 293(2) K, m(Mo Ka ) = 1.882 mm À1 , 1 calcd = 1.355 gcm À3 ,3 4519 reflections measured (5.9988 2q 558), 17 343 of which were unique (R int = 0.0463, R sigma = 0.0671) and were used in all calculations. The final R 1 was 0.0428 [I > 2 s(I)] and wR 2 was 0.1038 (all data).…”

“…Reported metallacycles includem etallabenzenes, [1,2] metallabenzynes, [3,4] metallaannulenes, [5] and other metallacycles. [6,7] Mosto ft hem are Hückel metallaaromatics. [8] Recently, we have prepared as eries of Craig-typeM çbiusm etallaaromatics, [9,10] in which metal centers are chelated by ac onjugated-carbon chain.T his conjugated-carbonc hain was called a "carbolong ligand",a nd its metalc helate complexa"carbolong complex".…”

Quantum‐chemical investigation of the phosphine ligand effects on the structure and electronic properties of a rhenabenzyne complex

“…3 ) 2 ]. [7] However, in recent years, numerous stable osmabenzynes have been isolated [8][9][10][11][12][13][14][15][16][17][18] and their interesting chemical properties have been determined. For instance, osmabenzynes such as metallabenzenes and aromatic compounds can undergo electrophilic substitution reactions.…”

“…The first stable metallabenzyne [Os(CC(SiMe 3 )C(CH 3 )C‐(SiMe 3 )CH)Cl 2 (PPh 3 ) 2 ] was unexpectedly obtained while trying to prepare osmium vinylidene complexes of the type [OsCl 2 (CCHR)(PR′ 3 ) 2 ]. [ 7 ] However, in recent years, numerous stable osmabenzynes have been isolated [ 8–18 ] and their interesting chemical properties have been determined. For instance, osmabenzynes such as metallabenzenes and aromatic compounds can undergo electrophilic substitution reactions.…”