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1.
A convenient synthesis of arachno-6,9-C2B8H14, based on the reduction of nido-5,6-C2B8H12 with sodium tetrahydroborate, is reported. Electrophilic halogenation of the former carborane produced a series of 1-X-6,9-C2B8H13 (X = Cl, Br and I) derivatives whose constitution was established on the basis of their 1H and 11B NMR spectra. 相似文献
2.
Young-hee Kim Paul A Cooke Robert Greatrex John D Kennedy Mark Thornton-Pett 《Journal of organometallic chemistry》1998,550(1-2)
[7,7-(PMe2Ph)2-9-(η6-isoPrC6H4Me)-7,9-PtRuB9H11] has a formal closo Wadian cluster-electron count, but a nido geometry, whereas [1-(η6-isoPrC6H4Me)-4,4-(PMe2Ph)2-1-4-RuPtB9H9], which does have a closo geometry, has a formal sub-closo cluster electron count; both compounds are formed in the reaction between [6-(η6-isoPrC6H4Me)-nido-6 RuB9H13], KH and [PtCl2(PMe2Ph)2]. 相似文献
3.
[(η5-C5R5)Fe(PMe3)2H] (R = H, Me) can be made in good yields in a simple one-pot reaction between FeCl2, PMe3, C5R5H (R = H, Me) and Na/Hg in thf. Reaction of [(η5-C5H5)Fe(PMe3)2H] with pentaborane(9) gives the known metallaborane [(η5-C5H5)-nido-2-FeB5H10] (1) in improved yield as well as the new metallaboranes [(η-C5H5)-nido-2-FeB5H8{μ-5,6-Fe(η5-C5H5)(PMe3)(μ-6,7-H)}] (2), [(η-C5H5)(PMe3)-arachno-2-FeB3H8] (3), [(η5-C5H5)2-capped-nido-2,3-Fe2B4H8] (4), [(η5-C5H5)-nido-2-FeB4H7(PMe3)] (5) and [(η5-C5H5)-nido-2-FeB5H8(PMe3)] (6). Reaction of [(η5-C5Me5)Fe(PMe3)2H] with pentaborane(9) gives predominantly [(η5-C5Me5)-nido-2-FeB5H10] (7) and [(η5-C5Me5)(PMe3)-arachno-2-FeB3H8] (8). Reaction of [(η5-C5H5)Fe(PMe3)2H] with 2 equiv. of BH3 · thf gives low yields of ferrocene and compound 3. Compound 7 thermally isomerises to the apical isomer [(η5-C5H5)-nido-2-FeB5H10] (9) in low yield. Compounds 1 and 7 deprotonate cleanly in the presence of KH at the unique B-H-B bridge to give [(η5-C5H5)-nido-2-FeB5H9−][K+] (10) and [(η5-C5Me5)-nido-2-FeB5H9−][K+] (11) respectively, whilst 6 deprotonates more slowly at one of two equivalent B-H-B bridges to give the fluxional anion [(η5-C5H5)-nido-2-FeB5H7(PMe3)−] (12). 相似文献
4.
One of the two bridging protons of the aza‐nido‐decaboranes RNB9H10X can be removed by certain bases to give nido‐anions [RNB9H9X]– [R/X = H/H ( 1 a ), Ph/H ( 1 b ), p‐MeC6H4/H ( 1 c ), Bzl/H ( 1 d ), H/N3 ( 1 ′ a )]; the stericly demanding base 1,8‐bis(dimethylamino)naphthalene (“proton sponge”, ps) is ideal. In the case of tBu anion, the deprotonation (→ C4H10) may be accompanied by a hydridation (→ C4H8), yielding the arachno‐anions [RNB9H11X]– ( 2 a , b , d , 2 ′ a ); these are the main products, when stericly non‐demanding bases like H– are applied. The Lewis acid BH3 is added to 1 a and 1 ′ a to give the aza‐arachno‐undecaborates HNB10H12X [X = H ( 3 a ), N3 (in position 2) ( 3 ′ a )]. Thia‐ and selenaaza‐arachno‐undecaborates, [S(RN)B9H10]– ( 4 b , c ) and [Se(RN)B9H10]– ( 4 ′ b , c ), are obtained from 1 b , c by the addition of sulfur or selenium, respectively. The methylation of the anions 4 c and 4 ′ c gives the thia‐ and selenaazaarachno‐undecaboranes (MeS)(RN)B9H10 ( 5 c ) and (MeSe)(RN)B9H10 ( 5 ′ c ), respectively. The action of HBF4 on the arachno‐borates [HNB10H12X]– ( 3 a , 3 ′ a ) leads to a mixture of nido‐HNB9H10X and nido‐HNB10H11X by the elimination of BH3 or H2, respectively; the aza‐nido‐decaborane predominates in the case of 3 ′ a and the aza‐nido‐undecaborane in the case of 3 a . The action of HBF4 on the anion 4 c yields the hypho‐undecaborate [S(RN)B9H10F2]– ( 6 c ). The structures of the products are elucidated on the basis of 1H and 11B NMR spectra, supported by 2D COSY and HMQC techniques. Two types of 11‐vertex‐arachno structures and an 11‐vertex‐hypho structure are found for the products. The crystal structures of 5 c and [Hps] 6 c · CH2Cl2 are reported. 相似文献
5.
Kolomnikova G. D. Petrovskii P. V. Sorokin P. V. Dolgushin F. M. Yanovsky A. I. Chizhevsky I. T. 《Russian Chemical Bulletin》2001,50(4):706-715
The reaction of OsCl2(PPh3)3 with [nido-7-R1-8-R2-C2B9H10]K+ produced a series of new exo-nido-osmacarborane complexes exo-nido-5,6,10-[Cl(Ph3P)2Os]-5,6,10-(-H)3-10-H-7-R1-8-R2-7,8-C2B9H6 (1: R1 = R2 = H; 2: R1 = R2 = Me; 3: R1 = R2 = PhCH2; 4: R1 + R2 = 1,2-C6H4(CH2)2; 5: R1 = H, R2 = Me) in which the osmium-containing group is linked to the nido-carborane ligand through three two-electron three-center bonds. Compounds 1—5 are formed as mixtures of symmetric (a) and asymmetric (b) isomers; pure symmetric isomers 2a and 4a were isolated by fractional crystallization, and the mixture of isomers 3a, was quantitatively separated into individual compounds 3a and 3b by column chromatography on silica gel. Detailed analysis of the 31P{1H}, 1H, 11B NMR spectra of 1a,b—5a,b and 2D 1H-1H{11B} and 11B{1H}-11B{1H} NMR spectra of 3a and 3b was performed. The structures of isomers 2a and 4a were confirmed by an X-ray diffraction study. According to the NMR and X-ray diffraction data, the isomerism of exo-nido-complexes 1a,b—5a,b is actually the cis—trans-isomerism of ligand arrangement in the octahedral coordination of the Os atom. 相似文献
6.
F. M. Dolgushin E. V. Balagurova I. V. Pisareva I. A. Godovikov I. G. Barakovskaya I. T. Chizhevsky 《Russian Chemical Bulletin》2013,62(8):1919-1923
A reaction of anhydrous CuCl2 with Na salts of the medium-cage carborane [7-X-nido-5,6-C2B8H10]?(X = H or I) derivatives in THF leads to new cupracarborane commo-clusters, [commo-9,9′-Cu(nido-7,8-C2B8H11)2]? and [commo-9,9′-Cu(11-I-nido-7,8-C2B8H10)2]?, in moderate yields. The clusters were isolated as stable [Ph3PEt]+ salts and characterized by 1H, 31P{1H}, and 11B/11B{1H} NMR spectroscopy and X-ray crystallography (for the unsubstituted derivative). The use in this reaction of the reducing agent Na2SO3 considerably increases the yields of both complexes from 25 and 18% to 74 and 68%, respectively. 相似文献
7.
Addition of the internal alkyne, 2-butyne, to nido-1,2-(Cp*RuH)2B3H7 (1) at ambient temperature produces nido-1,2-(Cp*Ru)2(μ-H)(μ-BH2)-4,5-Me2-4,5-C2B2H4 (2), nido-1,2-(Cp*RuH)2-4,5-Me2-4,5-C2B2H4 (3), and nido-1,2-(Cp*RuH)2-4-Et-4,5-C2B2H5 (4), in parallel paths. On heating, 2, which contains a novel exo-polyhedral borane ligand, is converted into closo-1,2-(Cp*RuH)2-4,5-Me2-4,5-C2B3H3 (5) and nido-1,6-(Cp*Ru)2-4,5-Me2-4,5-C2B2H6 (6) the latter being a framework isomer of 3. Heating 2 with 2-butyne generates nido-1,2-(Cp*RuH)2-3-{CMeCMeB(CMeCHMe)2}-4,5-Me2-4,5-C2B2H3 (7) in which the exo-polyhedral borane is triply hydroborated to generate a boron bound ---CMeCMeB(CMeCHMe)2 cluster substituent. Along with 3, 4, 5, 6, and 7, the reaction of 1 with 2-butyne at 85 °C gives closo-1,7-(Cp*Ru)2-2,3,4,5-Me4-6-(CHMeCH2Me)-2,3,4,5-C4B (8). Reaction of 1 with the terminal alkyne, phenylacetylene, at ambient temperature permits the isolation of nido-1,2-(Cp*Ru)2(μ-H)(μ-CHCH2Ph)B3H6 (9) and nido-1,2-(Cp*Ru)2(μ-H)(μ-BH2)-3-(CH2)2Ph-4-Ph-4,5-C2B2H4 (11). The former contains a Ru---B edge-bridging alkylidene fragment generated by hydrometallation on the cluster framework whereas the latter contains an exo-polyhedral borane like that of 2. Thermolysis of 11 results in loss of hydrogen and the formation of closo-1,2-(Cp*RuH)2-3-(CH2)2Ph-4-Ph-4,5-C2B3H3 (12). 相似文献
8.
Maria B Ezhova Hongming Zhang John A Maguire Narayan S Hosmane 《Journal of organometallic chemistry》1998,550(1-2)
The reaction of gaseous HCl with either the disodium or dilithium compound of the [nido-2,4-(SiMe3)2-2,4-C2B4H4]2− dianion (I) in 1:1 stoichiometry in THF produced the monoprotonated species 1-Na(THF)2-2,4-(SiMe3)2-2,4-C2B4H5 (II) or 1-Li(THF)2-2,4-(SiMe3)2-2,4-C2B4H5 (III), in 81% and 80% yields, respectively. This method proved superior to that involving the direct reduction of the closo-C2B4 carborane by metal hydrides. II and III were characterized by elemental analysis, 1H, 11B and 13C NMR and IR spectra. Compound II was recrystallized from a mixture THF, hexane and TMEDA (1:2:1) to isolate colorless crystals of the mixed solvated species, 1-(THF)-1-(TMEDA)-1-Na-2,4-(SiMe3)2-2,4-C2B4H5 (IV), which were subsequently used for X-ray diffraction studies. The structure of IV showed that the capping metal occupied the apical position above the open C2B3 face of the carborane and that a hydrogen atom was bridging the two adjacent boron atoms on that face. The 11B and 13C NMR spectra calculated by GIAO (gauge independent atomic orbital) methods at the 6-311G** level on the B3LYP/6-31G* optimized geometries of I–III, and a number of related nido- and closo-carboranes, gave excellent agreement with experiment, even in compounds where electron correlation effects are known to be important. 相似文献
9.
Michael A. Beckett Norman N. Greenwood John D. Kennedy Mark Thornton-Pett 《Polyhedron》1985,4(3):505-511
The compound [μ-2,7-(SCSNEt2)-7-(PMe2Ph)-nido-7-PtB10H11] has been obtained in a yield of 52% from the reaction of [7,7-(PMe2Ph)-nido-7-PtB10H12] and [AuBr2(S2CNEt2)], and identified by single crystal X-ray diffraction analysis and multi-element single and double resonance NMR spectroscopy. The yellow-orange compound crystallizes in the monoclinic space group P21/n with a 1179.2(2), b = 1244.9(5), c = 1641.4(2) pm, β = 95.45(1)°, Z = 4, and the structure (R 0.0209, Rw = 0.0211 for 3719 observed reflections) is that of a nido-7-platinaundecaborane with an exopolyhedral N,N-diethyldithiocarbamate ligand bridging the Pt(7) and B(2) positions to give a five-membered ring. The tetrahapto platinum-to-borane bonding has a considerable twist distortion relative to other nido-7-platinaundecaboranes which do not possess this cyclic feature. The NMR parameters exhibit no anomalies and are consistent with the crystal molecular structure. A plot of δ(11B) vs δ(1H) for directly bound exo-terminal hydrogen atoms shows good correlation with the slope 16 : 1. 相似文献
10.
A. V. Safronov M. N. Sokolova E. V. Vorontsov P. V. Petrovskii I. G. Barakovskaya I. T. Chizhevsky 《Russian Chemical Bulletin》2004,53(9):1954-1957
The reactions of a complex [(4-C7H8)RhCl]2 (C7H8 is norbornadiene) with salts of substituted nido-dicarbaundecaborates, [K][nido-7-R1-8-R2-7,8-C2B9H10] (R1 = R2 = H (a); R1 = R2 = Me (b); R1, R2 = 1,2-(CH2)2C6H4 (c); R1 = Me, R2 = Ph (d)), in CH2Cl2 afforded new closo-(2,3-(4-vinylcyclopenten-3-yl))rhodacarboranes. The structures of the compounds were studied by multinuclear NMR spectroscopy. A probable mechanism of the rearrangement of the norbornadiene ligand is discussed.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1875–1878, September, 2004. 相似文献
11.
Benedikt Schwarze Sebastian Sobottka Robert Schiewe Prof. Dr. Biprajit Sarkar Prof. Dr. Dr. h.c. Evamarie Hey-Hawkins 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(36):8550-8559
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). 相似文献
12.
Sergey V. Timofeev Elena A. Rakova Zoya A. Starikova Ivan A. Godovikov Vladimir I. Potkin Igor B. Sivaev Vladimir I. Bregadze 《Journal of organometallic chemistry》2007,692(23):5133-5140
Halogenation of 9-dimethylsulfonium-7,8-dicarba-nido-undecaborane [9-SMe2-7,8-C2B9H11] with N-chlorosuccinimide, bromine and iodine gave the expected corresponding halogen derivatives [9-SMe2-11-X-7,8-C2B9H10], where X = Cl (1), Br (2), I (3). In the bromination reaction, [9-SMe2-6-Br-7,8-C2B9H10] (4) was isolated as a minor product being the first example of substitution at a “lower” belt of the 7,8-dicarba-nido-undecaborate cage. The use of excess of bromine resulted in dibromo derivative [9-SMe2-6,11-Br2-7,8-C2B9H9] (5). Structures of the compounds prepared were determined using 11B-11B COSY NMR spectroscopy (for all halogen derivatives) and single crystal X-ray diffraction (for compounds 2, 3, and 5). 相似文献
13.
Kwok W. Chiu Henry S. Rzepa Richard N. Sheppard Geoffrey Wilkinson Wai-Kwok Wong 《Polyhedron》1982,1(11-12)
Neutral mononuclear tertiary phosphine rhodium(I) complexes of the formula RhX(PMe3)(dppm), X = Cl, CH2SiMe3, CH2CMe3, CH2CMe2Ph, η5-C5H5, DPPM = bis(diphenylphosphino)methane, RhCl(PPh3)(dppm), RhX(dppm)2, X = Cl, Me and Rh(η5-C5H5(dppm) have been synthesised. In Rh(η5-C5H5)(PMe3)(dppm), the dppm ligand is unidentate according to 31P{1H} NMR and X-ray data.The 31P{1H} NMR spectral parameters of RhX(PR3)(dppm) have been determined by a combination of two dimensional δ/J resolved spectroscopy and heteronuclear nuclear Overhauser effect difference spectroscopy (NOEDS) in conjunction with iterative analysis of the one dimensional spectra. 相似文献
14.
Addition of ethynylferrocene to nido-1,2-(Cp∗RuH)2B3H7 (1) at ambient temperature leads to nido-1,2-(Cp∗Ru)2(1,5-μ-C{Fc}Me)B3H7 (2, 3) and closo-4-Fc-1,2-(Cp∗RuH)2-4,6-C2B2H3 (4). Compounds 2 and 3 represent a pair of geometric isomers, nido-species in which the regiochemistry of the alkyne reduction conforms to the Markovnikoff rule. Compound 4 is an octahedral structure in which the inserted alkyne is on an open face of the closo cluster. 相似文献
15.
《Journal of organometallic chemistry》1993,447(2):C14-C17
Reaction of cis-Pt(PMe2Ph)2Cl2 with Tl2[7-Ph-7,8-nido-C2B9H10] affords 1-Ph-3,3-(PMe2Ph)2-3,1,2-PtC2B9H10, mild thermolysis (55°C) of which yields 1-Ph-3,3-(PMe2Ph)2-3,1,11-PtC2B9H10 and 11-Ph-3,3-(PMe2Ph)2-3,1,11-PtC2B9H10. Both of the latter compounds are produced by the microwave irradiation of a mixture of cis-Pt(PMe2Ph)2Cl2 and [HNMe3][7-Ph-7,8-nido-C2B9H11]. When cis-Pt(PMe2Ph)2Cl2 is allowed to react with Tl2[7,8-Ph2-7,8-nido-C2B9H9] at room temperature the only isolable species is 1,11-Ph2-3,3-(PMe2Ph)2-3,1,11-PtC2B9H9. The generation of rearranged products with 3,1,11-PtC2B9 architectures is inconsistent with a diamond-square-diamond mechanism for the isomerisation of icosahedral heteroboranes. 相似文献
16.
The volatile intermediate Et3NBH3 was isolated during the thermolysis of Et4NBH4 at 185°C for 16 hr under dynamic vacuum. The rate of decomposition of Et4NBH4 was studied. Separate thermolyses of Et4NBH4 (or Et3NBH3) with closo B9H92?nido B9H?12, or arachno B9H14? did not produce B10H102? as the major product. These results are inconsistent with the “build-up” mechanism previously proposed for the thermolytic convertion of BH 4? to B10H102? and a new mechanism is required. 相似文献
17.
M.Sc. Jan Schulz Dr. Menyhárt B. Sárosi Prof. Dr. Evamarie Hey-Hawkins 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(34):e202200531
The primary phosphines MesPH2 and tBuPH2 react with 9-iodo-m-carborane yielding B9-connected secondary carboranylphosphines 1,7-H2C2B10H9-9-PHR (R=2,4,6-Me3C6H2 (Mes; 1 a ), tBu ( 1 b )). Addition of tris(pentafluorophenyl)borane (BCF) to 1 a , b resulted in the zwitterionic compounds 1,7-H2C2B10H9-9-PHR(p-C6F4)BF(C6F5)2 ( 2 a , b ) through nucleophilic para substitution of a C6F5 ring followed by fluoride transfer to boron. Further reaction with Me2SiHCl prompted a H−F exchange yielding the zwitterionic compounds 1,7-H2C2B10H9-9-PHR(p-C6F4)BH(C6F5)2 ( 3 a , b ). The reaction of 2 a , b with one equivalent of R'MgBr (R’=Me, Ph) gave the extremely water-sensitive frustrated Lewis pairs 1,7-H2C2B10H9-9-PR(p-C6F4)B(C6F5)2 ( 4 a , b ). Hydrolysis of the B−C6F4 bond in 4 a , b gave the first tertiary B-carboranyl phosphines with three distinct substituents, 1,7-H2C2B10H9-9-PR(p-C6F4H) ( 5 a , b ). Deprotonation of the zwitterionic compounds 2 a , b and 3 a , b formed anionic phosphines [1,7-H2C2B10H9-9-PR(p-C6F4)BX(C6F5)2]−[DMSOH]+ (R=Mes, X=F ( 6 a ), R=tBu, X=F ( 6 b ); R=Mes, X=H ( 7 a ), R=tBu, X=H ( 7 b )). Reaction of 2 a , b with an excess of Grignard reagents resulted in the addition of R’ at the boron atom yielding the anions [1,7-H2C2B10H9-9-PR(p-C6F4)BR’(C6F5)2]− (R=Mes, R’=Me ( 8 a ), R=tBu, R’=Me ( 8 b ); R=Mes, R’=Ph ( 9 a ), R=tBu, R’=Ph ( 9 b )) with [MgBr(Et2O)n]+ as counterion. The ability of the zwitterionic compounds 3 a , b to hydrogenate imines as well as the Brønsted acidity of 3 a were investigated. 相似文献
18.
M. M. Il'in T. V. Zinevich I. V. Pisareva I. T. Chizhevsky V. A. Davankov 《Russian Chemical Bulletin》2000,49(4):759-760
Racemiccloso-rhodacarboranes,vis.
closo-(η3,2-C7H3-2-CR
2
1
)-1-R2-2-R3-3,1,2-RhC2B9H9 (R1=R2=R3=H; R1=H, R2=R3=Me; R1=R2=R3=Me) and (closo-2,2-(η3,2-C7H7-2-CH2)-2,1,7-RhC2B9H11), were successfully separated into enantiomers by high-performance liquid chromatography (HPLC).
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 759–761, April, 2000. 相似文献
19.
《Polyhedron》1987,6(9):1737-1740
The AlX3-catalyzed (X = Cl, Br, and I) halogenation of arachno-4,5-C2B7H13 with anhydrous hydrogen halides produces a series of 6-substituted derivatives, 6-X-4,5-C2B7H12. The same compounds along with 6,8-I2-4,5-C2B7H11 are obtained in non-catalyzed reactions with elemental halogens. The electrophile-induced nucleophilic substitution concept (EINS) of the substitution with hydrogen halides is suggested. The constitution of all compounds isolated was unambiguously determined via 1H, 13C, 11B, and two-dimensional (2-D) 11B-11B NMR spectra. 相似文献
20.
Simon Doherty Julian G. Knight Tom H. Scanlan Mark R. J. Elsegood William Clegg 《Journal of organometallic chemistry》2002,650(1-2):231-248
The aprotic and protic bi- and multidentate iminophosphines 2-Ph2PC6H4N=CR1R2 (R1=H, R2=Ph=2a; R1=Me R2=Ph=2b; R1=H, R2=2-thienyl=2c; R1=H, R2=C6H4-2-PPh2=2d; R1=H, R2=C6H4-2-OH=2e, R1=H, R2=C6H4-2-OH-3-But=2f; R1=H, R2=CH2C(O)Me=2g) have been prepared by the acid catalyzed condensation of 2-(diphenylphosphino)aniline with the corresponding aldehyde–ketone. Iminophosphine 2d can be reduced with sodium cyanoborohydride to give the corresponding amino-diphosphine 2-Ph2PC6H4N(H)CH2C6H4-2-PPh2 (2h). In the presence of a stoichiometric quantity of acid, 2-(diphenylphosphino)aniline reacts in an unexpected manner with benzaldehyde, salicylaldehyde, or acetophenone to give the corresponding 2,3-dihydro-1H-benzo[1,3]azaphosphol-3-ium salts and with pyridine-2-carboxaldehyde to give N-(pyridin-2-ylmethyl)-2-diphenylphosphinoylaniline, the latter of which has been characterized by single-crystal X-ray crystallography, as its palladium dichloride derivative. The attempted condensation of 2-(diphenylphosphino)aniline with pyridine-2-carboxaldehyde to give the corresponding pyridine-functionalized iminophosphine resulted in an unusual transformation involving the diastereoselective addition of two equivalents of aldehyde to give 1,2-dipyridin-2-yl-2-(o-diphenylphosphinoyl)phenylamino-ethanol, which has been characterized by a single-crystal X-ray structure determination. The bidentate iminophosphine 2-Ph2PC6H4N=C(H)Ph reacts with [(cycloocta-1,5-diene)PdClX] X=Cl, Me) to give [Pd{2-Ph2PC6H4N=C(H)Ph}ClX] and the imino-diphosphine 2-Ph2PC6H4N=C(H)C6H4-PPh2 reacts with [(cycloocta-1,5-diene)PdClMe] to give [Pd{2-Ph2PC6H4N=C(H)C6H4---PPh2}ClMe] and each has been characterized by single-crystal X-ray crystallography. The monobasic iminophosphine 2-Ph2PC6H4N=C(Me)CH2C(O)Me reacts with [Ni(PPh3)2Cl2] in the presence of NaH to give the phosphino–ketoiminate complex [Ni{2-Ph2PC6H4N=C(Me)CHC(O)Me}Cl], which has been structurally characterized. Mixtures of iminophosphines 2a–h and a palladium source catalyze the Suzuki cross coupling of 4-bromoacetophenone with phenyl boronic acid. The efficiency of these catalysts show a marked dependence on the palladium source, catalysts formed from [Pd2(OAc)6] giving consistently higher conversions than those formed from [Pd2(dba)3] and [PdCl2(MeCN)2]. Catalysts formed from neutral bi- and terdentate iminophosphines 2a–d gave significantly higher conversions than those formed from their monobasic counterparts 2e–f. Notably, under our conditions the conversions obtained with 2a–c compare favorably with those of the standards; catalysts formed from tris(2-tolyl)phosphine and tris(2,4-di-tert-butylphenyl)phosphite and a source of palladium. In addition, mixtures of [Ir(COD)Cl]2 and 2a–h are active for the hydrosilylation of acetophenone; in this case catalysts formed from monobasic iminophosphines 2e–f giving the highest conversions. 相似文献