The Sting of the Scorpion: A Metallaboratrane

Hill, Anthony F.; Owen, Gareth R.; White, Andrew J. P.; Williams, David J.

doi:10.1002/(sici)1521-3773(19990917)38:18<2759::aid-anie2759>3.0.co;2-p

Cited by 341 publications

(237 citation statements)

References 6 publications

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“…Analogous short Ba/H-B contacts (2.706 and 2.728Å) are obtained due to the secondary interaction between the barium ion and one hydrogen atom from the BH 2 group. Such alkaline earth metal and hydrogen interactions are observed in complex [M{N (2,4,6-Me 3 C 6 H 2 )-SiMe 3 } 2 (PMTDA)] (M ¼ Sr, Ba and PMDTA ¼ N,N,N 0 ,N 00 ,N 00 pentamethyldiethylenetriamine) and reported in literature. 23…”

Section: Alkaline Earth Metal Complexessupporting

confidence: 59%

Heavier group 2 metal complexes with a flexible scorpionate ligand based on 2-mercaptopyridine

et al. 2015

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We report the synthesis of novel alkaline earth metal complexes [k 2 -SS-(Bmp) 2 M(THF) n ] [M ¼ Ca (2), Sr (3) n ¼ 2; M ¼ Ba (4), n ¼ 3] of a flexible dihydrobis(2-thiopyridone)borate (Bmp) ligand based on 2mercaptopyridine. Complexes 2-4 were isolated in good yield by the reaction between sodium dihydrobis(2-thiopyridone)borate, [{(Bmp)Na(THF)} 2 ] n (1) and the corresponding alkaline earth metal diiodides in toluene at ambient temperature. The solid-state structures of the strontium and barium complexes, complexes 3 and 4 respectively, were established using single-crystal X-ray diffraction analysis. The solid-state structure of sodium complex 1 was also confirmed using X-ray techniques. The solid-state structures of complexes 3 and 4 revealed that the Bmp ligand coordinates through sulphur atoms to the metal ions in k 2 fashion. The strontium ion is attached symmetrically and the barium ion is asymmetrically linked with the Bmp ligand, manifesting the 2-thiopyridone and pyridine-2-thiolate tautomeric form of the Bmp ligand. The strontium ion in complex 3 adopts a distorted octahedral geometry whereas the geometry around the barium ion can best be described as a distorted pentagonal bipyramidal. Both complexes 3 and 4 also have a short B/H/M interaction due to the presence of the BH 2 group in the ligand. In the solid state, sodium complex 1 is polymeric in nature and in the asymmetric unit each sodium ion is bonded to two sulphur atoms through h 1 and m 2 modes. The adjacent BH 2 group is also linked with each sodium ion through hydrogen atoms via m 2 and h 1 .Scheme 3 Synthesis of alkaline earth metal complexes 2-4. 51416 | RSC Adv., 2015, 5, 51413-51420This journal is

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Section: Alkaline Earth Metal Complexessupporting

confidence: 59%

Heavier group 2 metal complexes with a flexible scorpionate ligand based on 2-mercaptopyridine

et al. 2015

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“…Later structural assignments, however, casted doubt on these complexes with negative results on metal‐LA interaction . It was not until 1999 that the first structural confirmation of a M→B dative bond was reported . Then, metal Lewis basicity has seen a prosper of research activity, and numerous novel Lewis pairs have been prepared featuring the interaction between Lewis basic transition metals and Lewis acidic ligands .…”

Section: Figurementioning

confidence: 99%

Realization of Lewis Basic Sodium Anion in the NaBH₃⁻ Cluster

et al. 2019

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We report a Na:−→B dative bond in the NaBH3− cluster, which was designed on the principle of minimum‐energy rupture, prepared by laser vaporization, and characterized by a synergy of anion photoelectron spectroscopy and electronic structure calculations. The global minimum of NaBH3− features a Na−B bond. Its preferred heterolytic dissociation conforms with the IUPAC definition of dative bond. The lone electron pair revealed on Na and the negative Laplacian of electron density at the bond critical point further confirm the dative nature of the Na−B bond. This study represents the first example of a Lewis adduct with an alkalide as the Lewis base.

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“…[1][2][3][4][5] As a complement to the ongoing work encompassing transition metal systems, our lab is interested in exploring the rich chemistry of heterobimetallic complexes involving a transition metal and a main group element, primarily aluminum. While analogous transitional metal-boron complexes have been studied extensively, [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] transition metal-aluminum heterobimetallics remain only sparsely investigated. [22][23][24][25][26][27][28][29][30][31][32][33][34] Aluminum is, however, of considerable interest as it is a potent Lewis acid and the most electropositive Group 13 element.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Electronic Characterization of Iridium‐Aluminum and Rhodium‐Aluminum Heterobimetallic Complexes Bridged by 3‐Oxypyridine and 4‐Oxypyridine

et al. 2020

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We demonstrate the synthesis and characterization of regioisomeric late transition metal‐aluminum heterobimetallic complexes containing 3‐ and 4‐oxypyridine ligands which bridge between the aluminum and transition metal center (Rh or Ir). Combined experimental and theoretical data allow for direct comparison of the electronic effect of the two different aluminum‐containing ligands on the late transition metal center. In combination with electronic data regarding previously reported 2‐oxypyridine bridged systems, we report a measurable decrease in ligand donor power as the regiosubstitution of the oxypyridine bridge is varied from 2‐ to 4‐ to 3‐. In all cases, addition of aluminum is found have a minimal effect on the donor ability of the oxypyridine bridge in dichloromethane solution.

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The Sting of the Scorpion: A Metallaboratrane

Cited by 341 publications

References 6 publications

Heavier group 2 metal complexes with a flexible scorpionate ligand based on 2-mercaptopyridine

Heavier group 2 metal complexes with a flexible scorpionate ligand based on 2-mercaptopyridine

Realization of Lewis Basic Sodium Anion in the NaBH₃⁻ Cluster

Synthesis and Electronic Characterization of Iridium‐Aluminum and Rhodium‐Aluminum Heterobimetallic Complexes Bridged by 3‐Oxypyridine and 4‐Oxypyridine

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The Sting of the Scorpion: A Metallaboratrane

Cited by 341 publications

References 6 publications

Heavier group 2 metal complexes with a flexible scorpionate ligand based on 2-mercaptopyridine

Heavier group 2 metal complexes with a flexible scorpionate ligand based on 2-mercaptopyridine

Realization of Lewis Basic Sodium Anion in the NaBH3− Cluster

Synthesis and Electronic Characterization of Iridium‐Aluminum and Rhodium‐Aluminum Heterobimetallic Complexes Bridged by 3‐Oxypyridine and 4‐Oxypyridine

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Realization of Lewis Basic Sodium Anion in the NaBH₃⁻ Cluster