Synthesis and reactivity of icosahedral molybdenum-monocarbaborane complexes containing one or two intramolecular amino bridgesThe new compounds described herein are based upon closo-1-carba-2-molybdenadodecaborane fragments, and all bear boron-bound exopolyhedral substituents. It should be noted that, although they contain chiral centres, species here occur as racemates. Substitued boron atoms at positions 3, 7, 11 or 6 could equally be labeled 6, 11, 7 and 3, respectively. In each case the former is used

Du, Shaowu; Kautz, Jason A.; McGrath, Thomas D.; Stone, F. Gordon A.

doi:10.1039/b208584b

Cited by 14 publications

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“…All four of the compounds 7f − j were readily identified by their spectroscopic properties (Tables and ). Their 11 B{ 1 H} NMR spectra confirm retention of molecular C s symmetry, with singlet resonances at δ 9.0 ( 7f ), 5.0 ( 7g ), and 8.2 ( 7h , j ) in the 11 B NMR spectra, these chemical shifts being typical in such systems for boron atoms with nitrogen-based functional groups attached. ,, The amine Me and Et moieties of 7f , g were recognized in 1 H and 13 C{ 1 H} NMR spectra, again in characteristic positions. Likewise, {N(Me)C(H)R} units were clearly evident in the spectra of 7h , j , but it was equally clear that these species differed from their precursors 7d , e , respectively: for example, their iminium N CH atoms resonate at δ 7.84 ( 7d ) versus 8.04 ( 7h ) and δ 7.67 ( 7e ) versus 7.89 ( 7j ) in 1 H NMR spectra and at δ 176.0 ( 7d ) versus 172.6 ( 7h ) and δ 181.2 ( 7e ) versus 177.7 ( 7j ) in 13 C{ 1 H} NMR spectra.…”

Section: Resultsmentioning

confidence: 79%

Revisiting [Mn(CO)₃(η⁵-nido-7,8-C₂B₉H₁₁)]^-, the Dicarbollide Analogue of [(η⁵-C₅H₅)Mn(CO)₃]: Reactivity Studies Leading to Boron Atom Functionalization

Hata

Kautz

et al. 2004

Organometallics

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Treatment of Na2[7,8-R2-nido-7,8-C2B9H9] (R = H, Me) with the reagent [Mn(NCMe)3(CO)3][PF6] affords the anions [3,3,3-(CO)3-1,2-R2-closo-3,1,2-MnC2B9H9]-, typically isolated as Cs+ or [N(PPh3)2]+ salts. These anions interact with cationic metal fragments {M(PPh3)}+ (M = Cu, Ag, Au) to give the bimetallic compounds [3,8-{M(PPh3)}-8-μ-H-3,3,3-(CO)3-1,2-R2-closo-3,1,2-MnC2B9H8], for which the structures of the Cu and Au species (R = H) have been confirmed by X-ray diffraction studies. In contrast, other electrophiles such as H+ and Me+ abstract hydride from carborane boron vertexes, which in the presence of donors (L) produces the neutral zwitterions [8-L-3,3,3-(CO)3-1,2-R2-closo-3,1,2-MnC2B9H8]. The halogenated derivatives [8-X-3,3,3-(CO)3-1,2-R2-closo-3,1,2-MnC2B9H8]- (X = Cl, Br, I) of the parent anions are obtained by hydride abstraction in halogenated solvents or by direct reaction with Br2 or I2. Moreover, further cluster functionalization is achieved by treating the 8-iodo species with the Grignard reagents R‘MgBr, leading to the anions [8-R‘-3,3,3-(CO)3-1,2-R2-closo-3,1,2-MnC2B9H8]-. When the substitution processes are repeated, the latter series of anions yield compounds with yet more functionality. Crystallographic studies of the boron-substituted derivatives [8-{(E)-N(Me)C(H)Me}-3,3,3-(CO)3-closo-3,1,2-MnC2B9H10], [N(PPh3)2][8-(p-C6H4Me)-3,3,3-(CO)3-1,2-Me2-closo-3,1,2-MnC2B9H8], and [4-{(Z)-N(Me)C(H)Me}-3,3,3-(CO)3-1,2,8-Me3-closo-3,1,2-MnC2B9H7] confirmed their structures and the sites of cage substitution.

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Section: Resultsmentioning

confidence: 79%

Revisiting [Mn(CO)₃(η⁵-nido-7,8-C₂B₉H₁₁)]^-, the Dicarbollide Analogue of [(η⁵-C₅H₅)Mn(CO)₃]: Reactivity Studies Leading to Boron Atom Functionalization

Hata

Kautz

et al. 2004

Organometallics

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“…Metallacarborane complexes containing monocarbollide ligands, derived from monocarbon carboranes, often retain an overall anionic charge as a consequence of the high formal charge (typically 3−) on the carborane fragment . While this feature may be useful in stabilizing the often unusual oxidation states accessible in such species, − its main utility lies in their reactions with electrophiles . With H + , for example, the metal center may simply be protonated to form a metal-hydride species, or the proton may behave as a hydride abstractor and thereby facilitate substitution at a {BH} vertex. − ,− Alternatively, when the electrophile is a cationic transition metal−ligand fragment, species containing multiple metal centers can result. ,5a,,,− …”

Section: Introductionmentioning

confidence: 99%

Construction of Metal Butterflies on a Metallacarborane Scaffold. 1. Synthesis and Structures of Bimetallic Precursors

McGrath

Hodson

et al. 2006

Organometallics

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Treatment of [N(PPh 3 ) 2 ][NEt 4 ][1,1,1-(CO) 3 -2-Ph-closo-1,2-MCB 9 H 9 ] (M ) Mn (1a), Re (1b)) with sources of the cations {M′(CO 2d)). In these, the {M(CO) 3 } fragment, formerly a cluster vertex, has assumed an exopolyhedral role, while the {M′(CO) 2 } units now occupy a site within the cluster. CompoundsRh (3d)) by deliberate CO addition or by CO scavenging. Reaction of 2b with PEt 3 gives [N(PPh 3 4), which has a mirror-symmetric structure, whereas 2a with NH 2 C 6 H 4 Me-1,4 affords 5), which is asymmetric. The structures of 2b, 3b, and 5 have been confirmed by X-ray diffraction studies.

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Spectroscopic and Electronic Properties of Molybdacarborane Complexes with Non‐innocently Acting Ligands

Schwarze

Sobottka

Schiewe

et al. 2019

Chemistry A European J

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The molybdacarboranes [3‐{L‐κ2N,N}‐3‐(CO)2‐closo‐3,1,2‐MoC2B9H11] (L=2,2′‐bipyridine (2,2′‐bpy, 1 a) or 1,10‐phenanthroline (1,10‐phen, 1 b)) incorporating well‐known potentially non‐innocent ligands (CO, 2,2′‐bpy, 1,10‐phen) and the “non‐spectator” nido‐carborane ([η5‐C2B9H11]2−) ligand were prepared and fully characterised. High‐resolution mass spectrometry, single‐crystal X‐ray diffraction methods, spectroscopy (IR, (resonance) Raman, NMR), cyclic voltammetry and spectroelectrochemistry (electrochemical properties) were supported by theoretical investigations of the electronic structure (DFT, CAS‐SCF, TD‐DFT).

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Cited by 14 publications

References 21 publications

Revisiting [Mn(CO)₃(η⁵-nido-7,8-C₂B₉H₁₁)]^-, the Dicarbollide Analogue of [(η⁵-C₅H₅)Mn(CO)₃]: Reactivity Studies Leading to Boron Atom Functionalization

Revisiting [Mn(CO)₃(η⁵-nido-7,8-C₂B₉H₁₁)]^-, the Dicarbollide Analogue of [(η⁵-C₅H₅)Mn(CO)₃]: Reactivity Studies Leading to Boron Atom Functionalization

Construction of Metal Butterflies on a Metallacarborane Scaffold. 1. Synthesis and Structures of Bimetallic Precursors

Spectroscopic and Electronic Properties of Molybdacarborane Complexes with Non‐innocently Acting Ligands

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Cited by 14 publications

References 21 publications

Revisiting [Mn(CO)3(η5-nido-7,8-C2B9H11)]-, the Dicarbollide Analogue of [(η5-C5H5)Mn(CO)3]: Reactivity Studies Leading to Boron Atom Functionalization

Revisiting [Mn(CO)3(η5-nido-7,8-C2B9H11)]-, the Dicarbollide Analogue of [(η5-C5H5)Mn(CO)3]: Reactivity Studies Leading to Boron Atom Functionalization

Construction of Metal Butterflies on a Metallacarborane Scaffold. 1. Synthesis and Structures of Bimetallic Precursors

Spectroscopic and Electronic Properties of Molybdacarborane Complexes with Non‐innocently Acting Ligands

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Revisiting [Mn(CO)₃(η⁵-nido-7,8-C₂B₉H₁₁)]^-, the Dicarbollide Analogue of [(η⁵-C₅H₅)Mn(CO)₃]: Reactivity Studies Leading to Boron Atom Functionalization

Revisiting [Mn(CO)₃(η⁵-nido-7,8-C₂B₉H₁₁)]^-, the Dicarbollide Analogue of [(η⁵-C₅H₅)Mn(CO)₃]: Reactivity Studies Leading to Boron Atom Functionalization