Synthesis and ligand substitution of tri-metallic triply bridging borylene complexes

Metal Rich Metallaboranes: Synthesis, Structure and Bonding of pileo-[(Cp*Ru)2M(CO)3(µ-H)(µ-E)(µ3-BH)B2H5] (M = Mo, W, E = CO, and M = Mn, E = H) Clusters

“…The two ruthenium atoms (apical and basal) are separated by an intermetallic distance of 2.7738(3) Å (2) and 2.7536(5) Å ( 4), which is in the typical range for a Ru-Ru single bond, but less compared to distances in homometallic pileo-[(Cp*Ru) 3 (µ-H) 2 (µ 3 -BX)B 2 H 5 ] (X = H (2.807 Å) [51], Cl (2.8323 Å) [47]. In addition, the observed B-B bond distances of 1.796(3) Å (2) and 1.781(8) Å (4) suggest the presence of B-B single bonds in 2 and 4 and comparatively less than in the similar clusters reported in Table 1 [47,51,52]. The core geometry of 2-4 is also comparable to the homo-and heterometallic clusters pileo-2,3-[{Fe(PMe [51], Cl [47], whereas this bond length is longer in the case of 2 (2.320 Å).…”

“…Three endo hydrogens and one CO in [53,54]. The existence of clusters 2-4 allows us to draw a structural comparison with the reported clusters with a similar geometry, but with different transition metals (Table 1) [47,51,52]. The axial Ru atom of the distorted square pyramid is situated approximately 1.804 Å (2) and 1.784 Å (4) above the RuMB 2 square plane, which is comparable to distances measured in the similar types of clusters shown in Table 1.…”

“…As shown in Figure 1, clusters 2 and 4 can be considered as adopting a nido-square pyramidal geometry capped by a BH fragment. The geometry of cluster 3 was established through the comparison of its spectroscopic data with cluster 2 and other similar pileo-trimetallic metallaboranes (Table 1) [47,51,52]. The structure of 3 seems similar to 2, and can also be considered as having a capped nido-square pyramidal Ru 2 MB 3 (M = Mo, W) geometry.…”

“…As shown in Figure 1, the orientations of the {Mo(CO) 3 } and {Mn(CO) 3 } fragments are different in 2 and 4. The orientation in 2 is similar to pileo-[(Cp*Rh) 2 {Cr(CO) 3 }(µ-CO)(µ 3 -BH)B 2 H 4 ] [47], whereas in 4, it is similar to that in pileo- [52]. In 2, the average Mo-B (2.383 Å) and Ru-Mo (2.849 Å) bond lengths are in accordance with those reported in molybdaboranes [52,58].…”

Synthesis of Trithia-Borinane Complexes Stabilized in Diruthenium Core: [(Cp*Ru)2(η1-S)(η1-CS){(CH2)2S3BR}] (R = H or SMe)

“…However, there is still little understanding of how a transition metal can be used to vary the chemistry of metallaborane compounds. In this regard, our group was actively involved in the synthesis of various electron-precise transition metal-boron complexes such as σ-borane [26][27][28][29][30][31], boryl [32,33], triply-bridged trimetallic borylene [34][35][36][37][38], diborane [39], B-agostic [26,27,[40][41][42], and metallaboratrane [26,27,43,44] complexes using of different synthetic precursors. An important aspect is the incorporation of transition metals into the chemistry of p-block elements other than carbon [45][46][47].…”