Substitution and insertion reactions of the dinuclear manganese µ-hydride complex [M₂(µ-H)(µ-PPh₂)(CO)₈]; crystal structures of the complexes [Mn₂(µ-σ:η²-CHCH₂)(µ-PPh₂)(CO)₇] and [Mn₂(µ-H)(µ-PPh₂)(CO)₆(CNBu^t)₂]

Abstract

Mn2(p-H)(p-PPh2)(C0)8] (1 ) has been synthesised in 80% yield from [Mn2(CO)10] and PHPh,. Reaction of (1) with RCN, RNC, PPh3, P(OMe)3, or (EtO),POP(OEt), gives substitution products of general formulae [Mn,(p-H)(p-PPh2)(C0)7L] [L = NCMe (2a) ; NCPh (2b) ; CNBu' (2c) ; CNCH2Ph (2d) ; PPh3 (2e) ; P(OMe), (2f) ; P(OEt), (2g)], [Mn,(p-H)(p-PPh,)(CO),L,] [L = CNBu' (3a) ; L2 = (EtO),POP(OEt), (3b)], and [Mn,(p-H)(p-PPh,) (CO),{(EtO)2POP(OEt)2}2] (4). Reaction of

A comparison between the reaction of P2Ph4 with [{Co2(CO)6}2(μ-η2:μ-η2-HOCH2CCCCCH2OH)] and the reaction of [Co2(μ-PPh2)2(CO)6] with HOCH2CCCCCH2OH

“…No coupling was resolved between the geminal vinyl protons. This correlates with other l-CR=CH 2 vinyl ligands for which negligible, or only a small coupling is observed [22][23][24][25][26][27][28]. The CH 2 protons of the lactone ring are observed as multiplets at d 4.32 and 4.18 with a geminal H-H coupling of 14 Hz and smaller unresolved coupling to both phosphorus atoms.…”

“…This is reflected in the slight asymmetry of the Co-P phosphido -Co bridge. The Co(2)-P(2) bond distance, 2.2461(7) Å , is thus shorter than the Co(4)-P(2) distance, 2.2676(7) Å , and the Co (2) [25][26][27][28]80,81]. Diyne functionalization by the phosphino group has taken place at one of the two outer diyne carbons as in the reaction of [{Co 2 (CO) 6 } 2 (l-g 2 :l-g 2 -Ph C"CAC"CPh)] with bma [3].…”

Structure of hexacarbonyl-μ-ethoxymethylidyne-μ-[σ:1–2-η-(1-phenyl-1-propenyl)]-diiron(Fe–Fe), C18H14Fe2O7

“…The molecule contains two organic bridges: 1-phenyl-l-propenyl and ethoxymethylidyne groups. The first is o bonded to Fe(2) with an Fe(2)-C(4) distance of 2.014 (10)/~ and unsymmetrically n bonded to Fe(1) with Fe(1)-C(4) 0.089 (21),/k shorter than Fe(1)--C(5), as is usual in other known complexes of this type (Iggo, Mays, Raithby & Hendrick, 1983 and references therein). The phenyl and methyl groups are in cis configuration, forming a torsion angle of-15.4 (9) °, similar to that observed in the 1,2-diphenylvinyl complex (Ros et al, 1985), where this angle is -13.1 °.…”

Substituted Metal Carbonyls. 27.1 Synthesis, Structures, and Metal−Metal Bonding of a Ferrocenylphosphine exo-Bridged Cluster with Two Heterometallic Triangles, [AuMn2(CO)8(μ-PPh2)]2(μ-dppf), and a Twisted-Bowtie Cluster, PPN+[Au{Mn2(CO)8(μ-PPh2)}2]- (dppf = 1,1‘-Bis(diphenylphosphino)ferrocene)

“…When an equimolar amount of [Au 2 (μ-dppf)](BF 4 ) 2 (generated in situ from Au 2 Cl 2 (μ-dppf) and AgBF 4 (1.0:2.6)) was added to 1 (from reduction of [Mn 2 (CO) 8 (μ-H)(μ-PPh 2 )] by NaBH 4 ), redox condensation resulted and [AuMn 2 (CO) 8 (μ-PPh 2 )] 2 (μ-dppf) ( 2 ) and AuCl(μ-dppf)[AuMn 2 (CO) 8 (μ-PPh 2 )] ( 3 ) were isolated in 51% and 13% yields, respectively. If AgBF 4 was omitted and the addition of the two substrates reversed, viz .…”

“…The IR bands in the carbonyl region of 2 and 3 are similar to those of (PPhR 2 )AuMn 2 (CO) 8 (μ-PPh 2 ) (R = Ph, Me 14 ) and Mn 2 (CO) 8 (μ-PPh 2 )(μ-H) …”