Diborylethylen‐Verbindungen als Liganden in Metallkomplexen, XIX. Neue Koordinationsvarianten des 2,3‐Dihydro‐1
            <i>H</i>
            ‐1,3‐diborols und 2,3‐Dihydro‐1
            <i>H</i>
            ‐1,3‐diborolyls in Platinkomplexen

Dedicated to Professor M . Frederick Hawthorne on the occasion of his 65th birthday Hawthorne et a1 reported the syntheses of the first complexes containing nido-C, B,H, ligands in 1965,['] thus heralding the beginnings of metallacarborane chemistry which they then systematically elaborated.[21 Of the smaller carboranes, the nido-C,B,H, ligand, which contains five less BH groups, also displays a high synthetic potential.[3] The metallacarborane clusters 1 and 2 (M = Fe, Co) are well-known complexes containing these ligands, and may-if regarded as x complexes-be considered as forming a bridge to the metallocenes. The iron compounds lc4] and 215] (M = Fe) are paramagnetic complexes (1 7 valence electrons (VE)), which react by taking up one additional electron to form the diamagnetic anions 1-and 2-(M = Fe), the analogues of ferrocene. The buildup of neutral 18 VE complexes requires either the substitution of the C,H, ligand by C,H,, or the replacement of the C,B, carboranes (n = 4, 9) by the 5e ligand nido-C,B,R,, which would lead to the formation of 3. We report here on the (tricarbahexaborany1)iron complex 3a which is analogous to ferrocene, and on the first 16 VE iron sandwich compound 7. 3We have observed the metal-induced formation of 2,3,5-tricarbahexaboranylnickel complexes[6] by rearrangement of bis(2,3-dihydro-l,3-diborole)nickel complexes at room temperature and have recently been able to synthesize the unknown 2,3,5-tricarbahexaborane 5 by two different routes. The hydroboration of 1,3-diethyl-2-methyl-4,5-diisopropylidene-l,3-diborolane (4) ['] with (HBEt,), leads rather surprisingly to a 2: 1 mixture of the carborane 5['] and the 1,3-diborole 6, which can be deprotonated to the corresponding anions (5-H)-and (6-H)-by the action of NaH or LiMe, respectively.

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(η³‐Allyl)nickel(μ,η⁵‐2,3‐dihydro‐1,3‐diborolyl)nickel(η³‐allyl)(η¹‐allyl)‐Tripeldecker‐Komplexe

Brodt

Kuhlmann

Siebert

1989

Chem. Ber.

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The tetra-and pentamethyl derivatives la, b of 2,3-dihydro-1,3-diborole react with an excess of bis(ally1)nickel at low temperature to give thermolabile tris(ally1)dinickel triple-decker complexes 2a, b with the 2,3-dihydro-1,3-diborolyl ligand in bridging position. 2a is more reactive than 2b with respect to a condensation to give the quadruple-decker complex 4. The spectroscopic data ('H, ''C NMR) show that one ally1 group is n-statically bound to a nickel atom, whereas the two others at the second nickel atom undergo a fast q1,q3 exchange with formation of an AMNXY spin system.

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Diborylethylen‐Verbindungen als Liganden in Metallkomplexen, XIX. Neue Koordinationsvarianten des 2,3‐Dihydro‐1 H ‐1,3‐diborols und 2,3‐Dihydro‐1 H ‐1,3‐diborolyls in Platinkomplexen

Cited by 11 publications

References 12 publications

(η⁵‐Pentamethylcyclopentadienyl)eisen‐Komplexe mit η⁵‐2,3,5‐Tricarbahexaboranyl‐ und mit η⁵‐2,3‐Dihydro‐1,3‐diborolyl‐Liganden

(η⁵‐Pentamethylcyclopentadienyl)eisen‐Komplexe mit η⁵‐2,3,5‐Tricarbahexaboranyl‐ und mit η⁵‐2,3‐Dihydro‐1,3‐diborolyl‐Liganden

(η⁵‐Pentamethylcyclopentadienyl)iron Complexes with η⁵‐2,3,5‐Tricarbahexaboranyl and η⁵‐2,3‐Dihydro‐1,3‐diborolyl Ligands

(η³‐Allyl)nickel(μ,η⁵‐2,3‐dihydro‐1,3‐diborolyl)nickel(η³‐allyl)(η¹‐allyl)‐Tripeldecker‐Komplexe

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Diborylethylen‐Verbindungen als Liganden in Metallkomplexen, XIX. Neue Koordinationsvarianten des 2,3‐Dihydro‐1 H ‐1,3‐diborols und 2,3‐Dihydro‐1 H ‐1,3‐diborolyls in Platinkomplexen

Cited by 11 publications

References 12 publications

(η5‐Pentamethylcyclopentadienyl)eisen‐Komplexe mit η5‐2,3,5‐Tricarbahexaboranyl‐ und mit η5‐2,3‐Dihydro‐1,3‐diborolyl‐Liganden

(η5‐Pentamethylcyclopentadienyl)eisen‐Komplexe mit η5‐2,3,5‐Tricarbahexaboranyl‐ und mit η5‐2,3‐Dihydro‐1,3‐diborolyl‐Liganden

(η5‐Pentamethylcyclopentadienyl)iron Complexes with η5‐2,3,5‐Tricarbahexaboranyl and η5‐2,3‐Dihydro‐1,3‐diborolyl Ligands

(η3‐Allyl)nickel(μ,η5‐2,3‐dihydro‐1,3‐diborolyl)nickel(η3‐allyl)(η1‐allyl)‐Tripeldecker‐Komplexe

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(η⁵‐Pentamethylcyclopentadienyl)eisen‐Komplexe mit η⁵‐2,3,5‐Tricarbahexaboranyl‐ und mit η⁵‐2,3‐Dihydro‐1,3‐diborolyl‐Liganden

(η⁵‐Pentamethylcyclopentadienyl)eisen‐Komplexe mit η⁵‐2,3,5‐Tricarbahexaboranyl‐ und mit η⁵‐2,3‐Dihydro‐1,3‐diborolyl‐Liganden

(η⁵‐Pentamethylcyclopentadienyl)iron Complexes with η⁵‐2,3,5‐Tricarbahexaboranyl and η⁵‐2,3‐Dihydro‐1,3‐diborolyl Ligands

(η³‐Allyl)nickel(μ,η⁵‐2,3‐dihydro‐1,3‐diborolyl)nickel(η³‐allyl)(η¹‐allyl)‐Tripeldecker‐Komplexe