1898-77-7

Upstream product

• 97012-38-9 trimethylphosphine-triborane adduct 
• 19287-45-7 diborane 
• 18433-84-6 pentaborane⁽¹¹⁾ 
• 39678-68-7 bis(trimethylphosphine)-diborane⁽⁴⁾ 
• 18283-93-7 tetraborane 
• 60-29-7 diethyl ether 
• 594-09-2 trimethylphosphane 
• 97551-46-7 trimethylamine-trimethylphosphine-diborane⁽⁴⁾ 
• 186084-09-3 [2,2,2-(PPh₃)2(CO)-nido-2-OsB₄H₇-3-BH₂*PMe₃] 
• 159472-53-4 [Cr(CO)5(η1-BH3(P(CH3)3))] 
• 159472-54-5 [W(CO)5(η1-BH3(P(CH3)3))] 
• 910468-99-4 [(C5H5)Ru(PMe3)2(η1-H3B*PMe3)][B(3,5-C6H3(CF3)2)4] 
• 536-74-3 phenylacetylene 
• 168000-42-8 hydrido(trimethylphosphane)tris(2,6-diisopropylphenyloxy)titanium(IV) 

Downstream Products

• 14044-65-6 borane-THF 
• 19624-22-7 pentaborane⁽⁹⁾ 
• 97012-38-9 trimethylphosphine-triborane adduct 
• 19287-45-7 diborane 
• 13283-31-3 borane 
• 594-09-2 trimethylphosphane 
• 591216-09-0 [(phenyl)2B(CH₂P(methyl)2(BH₃))2][Li(N,N,N',N'-tetramethylethylenediamine)] 
• 566933-64-0 Mn(CO)4(BH₃P(CH₃)3)(P(CH₃)2(C₆H₅))⁽¹⁺⁾*B(C₆H₃(CF₃)2)4^(1-)=[Mn(CO)4(BH₃P(CH₃)3)(P(CH₃)2(C₆H₅))][B(C₆H₃(CF₃)2)4] 
• 566933-67-3 Mn(CO)4(BH₃P(CH₃)3)(P(C₂H₅)3)⁽¹⁺⁾*B(C₆H₃(CF₃)2)4^(1-)=[Mn(CO)4(BH₃P(CH₃)3)(P(C₂H₅)3)][B(C₆H₃(CF₃)2)4] 
• 910468-99-4 [(C5H5)Ru(PMe3)2(η1-H3B*PMe3)][B(3,5-C6H3(CF3)2)4] 
• 910469-01-1 [(C5Me5)Ru(PMe3)2(η1-H3B*PMe3)][B(3,5-C6H3(CF3)2)4] 
• 1189780-31-1 ((CH₃)2C₆H₅Si)CH₂P(BH₃)(CH₃)2 

Relevant academic research and scientific papers

Synthesis, structural characterization, and cyclometalation chemistry of tantalum terphenyl compounds

The κ1-m-terphenyl complex of tantalum, [ArTol2]Ta(NMe2)3Cl ([ArTol2] = 2,6-di-p-tolylphenyl), has been synthesized by the reaction of [Ta(NMe2)3Cl2]2 with two equivalents of [ArTol2]Li. [ArTol2]Ta(NMe2)3Cl provides access to a variety of monoalkyl compounds, [ArTol2]Ta(NMe2)3R (R = Me, Et, Prn, Bun, and Np; Np = CH2BuT), via the reactions with the corresponding RLi. In addition, the reaction of [Ta(NMe2)3Cl2]2 with excess [ArTol2]Li affords the bis(terphenyl) complex, [ArTol2]2Ta(NMe2)3, while the reaction of [ArTol2]Ta(NMe2)3Cl with LiBH4 gives the borohydride complex, [ArTol2]Ta(NMe2)3(κ2-BH4). The dichloride compound, [ArTol2]Ta(NMe2)2Cl2, which is obtained via the reaction of [ArTol2]Ta(NMe2)3Cl with Me3SiCl, provides access to a series of dialkyl derivatives, [ArTol2]Ta(NMe2)2R2 (R = Me, Et, Prn, Bun, and Np), via the reactions with the corresponding RLi. The κ1-m-terphenyl ligands in these complexes are susceptible to metalation. Thus, [ArTol2]Ta(NMe2)3R eliminates RH to afford [κ2-ArTol,Tol′]Ta(NMe2)3 (Tol′ = C6H3Me), while [ArTol2]Ta(NMe2)2Np2 eliminates NpH to form [κ2-ArTol,Tol′]Ta(NMe2)2Np.

Tris(2,6-diisopropylphenolato)titanium(IV) dihydridodiorganylborates: Synthesis and structures

The reactions of tris(2,6-diisopropylphenolato)titanium(IV) chloride with alkali-metal dihydridodiorganylborates M(H2BR2) (M = Li, K; R = Me, C6H11, CMe3; BR2 = BC5H10, BC8H14) led to the corresponding titanium dihydridodiorganylborates. However, in almost all cases byproducts such as (2,6-diisopropylphenolato)diorganylboranes, triorganylboranes, diorganylboranes, diborane and tetrakis(2,6- diisopropylphenolato)titanium(IV) were also generated. (2,6-iPr 2C6H3O)3Ti(H2BR 2) compounds also resulted from the interaction of methyltris(2,6-diisopropylphenolato)titanium, for example, with catecholborane. In addition to the formation of tris(2,6-diisopropylphenolato) catecholboratotitanium(IV), B-methylcatecholborane was also formed The reaction of potassium dihydro-9-cyclooctylborate with 2,6-bis(2,2-di-tert-butyl-2- hydroxyethyl)pyridinetitanium dichloride (LTiCl2) led to the complex LTi(H2BC8H14)2. This compound showed no agostic C-H···Ti interaction in contrast to (2,6-iPr2C6H3O)3TiH 2BC8H14 and the corresponding titanium dihydridobis(cyclohexyl)borate.

Syntheses and reactivity of cationic borane-ruthenium complexes [(η5-C5R5)Ru(PMe3) 2(η1-BH3·EMe3)][BAr 4f] (R = H, Me; e = N, P; BAr4f = [B{3,5-C6H3(CF3)2}4])

Chloride displacement from [(η5-C5R 5)Ru(PMe3)2Cl] by Na[BAr4 f] in the presence of BH3·EMe3 afforded cationic borane σ complexes containing an unsupported B-H-Ru bridge, [(η5-C5R5)Ru(PMe3) 2(η1-BH3·EMe3)][BAr 4f] (4a: R = H, EMe3 = PMe3; 4b: R = Me, EMe3 = PMe3; 4c: R = H, EMe3 = NMe 3; [BAr4f] = [B{3,5-C6H 3(CF3)2}4]). Compounds 4a-c were fully characterized, and their structures were determined by X-ray crystallographic analysis. In these complexes, the borane ligand is coordinated to the ruthenium atom through a B-H-Ru three-center two-electron bond. They exhibit fluxional behavior due to site exchange between the BH hydrogen atoms. Complexes 4a and 4c are remarkably stable. However, they are hydrolyzed by a trace amount of water to produce a cationic dihydride, trans-[CpRuH 2-(PMe3)2]+ (6, Cp = η5-C5H5). The reactivity of 4a toward various substrates was investigated.

Coordination compounds of monoborane - Lewis base adducts: Syntheses and structures of [M(CO)5(η1-BH3·L)] (M = Cr, Mo, W; L = NMe3, PMe3, PPh3)

Photolysis of [M(CO)6] (M = Cr, W) in the presence of BH3·L (L = NMe3, PMe3, PPh3) gave isolable borane complexes [M(CO)5(η1-BH3·L)] (1a, M = Cr, L = PMe3; 1b, M = Cr, L = PPh3; 1c, M = Cr, L = NMe3; 2a, M = W, L = PMe3; 2b, M = W, L = PPh3; 2c, M = W, L = NMe3). In products 1 and 2, the monoborane - Lewis base adduct coordinates to the metal center through a B-H-M three-center two-electron bond, which was confirmed by X-ray structural analyses of 1a, 2a, and 2b at low temperature. The X-ray crystal structural analysis of 1c at ambient temperature also showed the same coordination mode, although the positions of hydrogen atoms on the boron were not determined. The 1H NMR spectra of 1 and 2 exhibit only one BH signal at -2 to -3 ppm with an intensity of 3H in the temperature range of -80 °C to room temperature. This indicates that the coordinated BH and terminal BH's are rapidly exchanging in solution even at low temperature. When [Mo(CO)6] was used as a precursor, the formation of the corresponding molybdenum - borane complexes, [Mo(CO)5(η1-BH3·L)] (3a, L = PMe3; 3b, L = PPh3; 3c, L = NMe3), was observed by NMR spectroscopy, but the complexes could not be isolated because of their thermal instability. Complexes of pyridineborane [M(CO)5(η1-BH3·NC5H 5)] (1d, M = Cr; 2d, M = W) were also observable by NMR spectroscopy. Fenske - Hall MO calculations for the model compound [Cr(CO)5(η1-BH3·PH3)] (1e) demonstrated that the bonding between the borane and metal can be described as donation of the bonding electron pair of BH to the a1 orbital of [Cr(CO)5], and that π back-donation from the metal d orbital to the antibonding σ* orbital of BH is negligible. Compounds 1-3 can be regarded as model compounds of the methane complex [M(CO)5(CH4)], which is observed in the photolyses of [M(CO)6] in methane matrixes. Structural and spectroscopic features of the ligated borane are discussed and compared with those of related compounds.

Degradation and Modification of Metallaboranes: Reactions of the Hexaborane(10) Analogue nido-(PPh3)2(CO)OsB5H9 with Phosphines and the Crystal and Molecular Structure of [2,2,2-(PPH3)2(CO)-nido-2-OsB4H7-3-BH2.PPh2.Me]

The reaction between the osmahexaborane [2,2,2-(PPh3)2(CO)-nido-2-OsB5H9] (1) and bases such as PPh3, PPh2Me, and PMe3 in refluxing CH2Cl2 affords unique adducts of the type [2,2,2-(PPh3)2(CO)-nido-2-OsB4H7-3-BH2.PR3] (2) for which spectroscopic data suggest the presence of a pendent boryl group. This was confirmed by a crystal structure determination for the PPh2Me adduct which shows that 2 is a nido-osmapentaborane with a terminal BH2.PPh2Me moiety on a basal boron atom adjacent to the metal. The reaction is reversible in the case of PPh3 and to a lesser extent PPh2Me, but not for PMe3. Heating the PPh3 adduct affords the osmahexaborane 1, liberating PPh3, but degradation to the osmapentaborane [2,2,2-(PPh3)2(CO)-nido-2-OsB4H8] (6) and BH3.PPh3 competes. The tendency to degrade to phosphine.borane increases markedly down the series R3 = Ph3, Ph2Me, and Me3. When the bidentate bases [1,2-(PPh2)2(CH2)2] and [1,3-(PPh2)2(CH2)3] (abbreviated as dppe and dppp, respectively) are used, two major products are observed in each case. One (3a) [2,2,2-(PPh3)2(CO)-nido-2-OsB4H7-3-(BH2.dppe)] (or 3b, BH2.dppp) is analogous to 2 with one end of the bidentate phosphine donor uncoordinated. In the other (4a) [2,2-(PPh3)(CO)-nido-2-OsB4H7-η(2)-3,2-(BH2.dppe)] (or 4b, BH2.dppp), the free end of the bidentate ligand has replaced a PPh3 group on Os. In the reaction of [(PPh2)2(CH2)] (abbreviated as dppm) with 1, only a species analogous to 3 is observed. The species 3b, the one involving dppp, has beenfurther modified at the free phosphine end of the ligand, to form [2,2, 2-(PPh3)2(CO)-nido-2-OsB4H7-3-(BH2.dppp.BH3)] (5).

UEBERGANGSMETALL-SUBSTITUIERTE PHOSPHANE, ARSANE UND STIBANE. XLVIII. BORIN-KOMPLEXE DER METALLO-PHOSPHANE Cp(CO)2(L)M-PPh2 (M=Mo, W; L=CO, Me3P)

The reaction of the metallophosphanes Cp(CO)2(L)M-PPh2 (1a-1c) (M=Mo, W; L=CO, Me3P) with H3B*THF yields the thermally stable borane adducts Cp(CO)2(L)-PPh2-BH3 (2a-2c), while with BF3*OEt2 the complex salts ;BF4 (3a-3c) are obtained.Th

Reaction of tetraborane(10) with trimethylphosphine in tetrahydrofuran

When tetraborane(10) was treated with trimethylphosphine in a 1:1 molar ratio in tetrahydrofuran at -90 to -70°C, (CH3)3P·BH3, THF·B3H7, and H2B(THF)2+B3H8 - were produced. The formation of (CH3)3P·B3H7 was minimal. The same reaction was performed in dimethyl ether, diethyl ether, and dichloromethane, and the patterns of product distribution were compared with each other. The previously proposed mechanism for the B4H10 cleavage reactions was used to explain the observed results by taking the effects of concentrations and strength of the reacting bases into consideration. This mechanistic model explained also the results of the reactions of B4H10 with trimethylamine and phosphine in tetrahydrofuran. The values of 4 ± 1 and 0.41 ± 0.02 were obtained as the equilibrium constants for (CH3)3P·BH3 + THF·B3H7 ? THF·BH3 + (CH3)3P·B3H7 at 25°C and H3P·BH3 + THF·B3H7 ? THF·BH3 + H3P·B3H7 at 0°C, respectively.