(.mu.-H)2M3(CO)8(.mu.-PPh2)2 (M = Fe, Ru, Os): an isostructural triad of phosphido-bridged hydrides. Rational synthesis and structural characterization

Abstract

= i-Pr), 97782-75-7; 2 (R = cyclohexyl, R' = (CH,),OAc), 97782-76-8; 2 (R = Ph, R' = i-Pr), 97782-77-9; 2 (R = Ph, R' = (CH,),OH), 97782-780; 2 (R = R' = i-Pr), 97782-79-1; 2 (R = t-Bu, 97782-80-4; MeB(OMe),, 7318-81-2; MeB(OEt),, 86595-26-8; ,, 86595-27-9; MeB(OBu-t),, 819-385; MeLi, 917-54-4; n-BuB(OPr-i),, 86595-32--methyl-1,3,2-dioxatetramethylborolane, 94242-85-0; 2-methyl-l,3,2-benzodioxaborole, 51901-49-6; 2-n-butyl-1,3,2-dioxaborinane, 30169-71-2; tert-butyl-1,3,2-dioxaborinane, 63689-73-6; cyclohexyldiisopropoxyborane, 97782-70-2; 2-cyclohexyl-1,3,2-dioxaborinane, 30169-75-6; 2-phenyl-1,3,2-dioxaborinane, 4406-77-3; n-butylisopropylisopropyborane, 97782-81-5; n-butyl-tert-butylisopropoxyborane, 97782-82-6; n-butylphenylisopropoxyborane, 97782-83-7; n-bu-R' = (CH,),OH), 97782-74-6; 2 (R = Ph, R' = (CH,),OH), tyl-tert-butyl(3-hydroxypropoxy)borane, 97782-84-8; n-butylphenyl(3-hydroxypropoxy)borane, 97782-85-9; n-butylisopropyl(3-hydroxypropoxy)borane, 97782-86-0; tert-butylisopropylisopropoxyborane, 97782-87-1; di-tert-butylisopropoxyborane, 86595-35-9; tert-butylphenylisopropoxyborane, 97782-88-2; di-tert-butyl(3-hydroxypropoxy)borane, 97782-89-3; tert-butylphenyl(3-hydroxypropoxy)borane, 97782-90-6; tert-butylisopropyl(3-hydroxypropoxy)borane, 97782-91-7; cyclohexylisopropylisopropoxyborane, 97782-92-8; tert-butylcyclohexylisopropoxyborane, 97782-93-9; phenylcyclohexylisopropoxyborane, 97782-94-0; tert-butylcyclohexyl(3-hydroxypropoxy)borane, 97782-95-1; isopropylcyclohexyl(3-hydroxypropoxy)borane, 97782-99-5; phenylcyclohexyl(3-hydroxypropoxy) borane, 97782-96-2; phenylisopropylisopropoxyborane, 97782-97-3; diphenylisopropoxyborane, 69737-51-5; isopropylphenyl(3-hydroxypropoxy)borane, 97782-98-4; diphenyl(3-hydroxypropoxy)borane, 74666-84-5; acetyl chloride, 75-36-5; benzoyl chloride, 98-88-4. (pH)2M3(C0)8(p-PPh2)2 (M = Fe, Ru, Os): An Isostructural Triad of Phosphido-Bridged Hydrides. Rational Synthesis and Structural CharacterizationT h e synthesis and structural characterization of t h e triad of phosphido-bridged hydrido clusters (p-H)2M3(CO)8(p-PPh2)2 (1, M = Fe, 2, M = Ru, and 3, M = Os) are described. T h e triiron cluster 1 has been prepared via the reaction of P h p H with the protonated anion Fe4(C0)12-. The ruthenium and osmium congeners have been obtained from the phosphine complexes M3(C0)10(PPh2H)2 via oxidative addition of the P-H bonds of the secondary phosphines to the clusters. Crystals of 1-3 are triclinic of space group Pi with unit cell dimensions. 1: a = 10.918 (2) A, b = 11.898 (2) A, c = 14.705 (2) A; a = 75.02 (l)', / 3 = 84.72 ( l ) ' , y = 70.84 ( 1 ) ' . 2: a = 11.150 (1) A, b = 12.027 (1) A, c = 14.693 (1) A; a = 76.03 (l)', p = 84.70 (l)', y = 70.24 (1)'. 3: a = 11.184 (1) A, b = 11.991 (1) A, c = 14.657 (1) A; a = 76.17 (l)', p = 84.72 ( I ) ' , y = 70.01 ( 1 ) ' . T h e structures were solved and refined t o the following R and R, values; 1, R = 0.034, R, = 0.039 on 4243 observed (I 1 3u(Z)) data; 2, R = 0.023, R, = 0.027 on 5478 data; 3, R = 0.038, R, = 0.048 on 5325 dat...

Interplay of Electronic and Steric Effects of R2PH (R = tBu, o‐tolyl) in Reactions with Triruthenium Dodecacarbonyl

“…The molecule consists of a triangular metal cluster core with three metal‐metal bonds. The structural parameters of 3 are in good accordance with the reported ones of [Ru 3 (μ‐H) 2 (μ‐PPh 2 ) 2 (CO) 8 ] and [Ru 3 (μ‐H) 2 (μ‐PCy 2 ) 2 (CO) 8 ] , …”

Synthesis, structure and reactivity of triosmium clusters derived from the reactions of [Os3(CO)10(μ-dppm)] (dppm = Ph2PCH2PPh2) and [Os3(μ-H)(CO)8{Ph2PCH2P(Ph)C6H4}] with PHPh2

“…The Os( 1)᎐P( 1) and Os( 2)᎐P( 1) distances are comparable with values observed for related molecules where a phosphido group bridges a strong metal-metal bond. 18,19,28 The Os᎐P distances involving the bridging dppm ligand 2.327(4) and 2.364(4) Å are also somewhat asymmetric and generally shorter than those involving the phosphide ligands; these values are also slightly shorter than the corresponding values in compound 3. As expected, the Os(1)᎐P( 1)᎐Os( 2) angle [74.34 (10)Њ] is much narrower than the Os(2)᎐P( 2)᎐Os( 3) angle [110.…”

Sawhorse-type diruthenium tetracarbonyl complexes

“…It was also obtained as a side-product in many reactions involving Ru 3 (CO) 12 and diphenylphosphine [78][79][80][81][82][83][84].…”